US11500289B2 - Positive resist composition and pattern forming process - Google Patents

Positive resist composition and pattern forming process Download PDF

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US11500289B2
US11500289B2 US16/708,851 US201916708851A US11500289B2 US 11500289 B2 US11500289 B2 US 11500289B2 US 201916708851 A US201916708851 A US 201916708851A US 11500289 B2 US11500289 B2 US 11500289B2
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group
bond
recurring units
resist composition
formula
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Jun Hatakeyama
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Shin Etsu Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C08F212/24—Phenols or alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G03F7/2006—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light using coherent light; using polarised light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2037—Exposure with X-ray radiation or corpuscular radiation, through a mask with a pattern opaque to that radiation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

Definitions

  • This invention relates to a positive resist composition and a patterning process using the composition.
  • next generation 7-nm node devices and next-but-one generation 5-nm node devices include extreme ultraviolet (EUV) lithography of wavelength 13.5 an and double patterning version of the ArF lithography, on which active research efforts have been made.
  • EUV extreme ultraviolet
  • the exposure system for mask manufacturing made a transition from the laser beam exposure system to the EB exposure system to increase the accuracy of line width. Since a further size reduction became possible by increasing the accelerating voltage of the electron gun in the EB exposure system, the accelerating voltage increased from 10 kV to 30 kV and reached 50 kV in the current mainstream system, with a voltage of 100 kV being under investigation.
  • Non-Patent Document 1 Since chemically amplified resist compositions are designed such that sensitivity and contrast are enhanced by acid diffusion, an attempt to minimize acid diffusion by reducing the temperature and/or time of post-exposure bake (PEB) fails, resulting in drastic reductions of sensitivity and contrast.
  • PEB post-exposure bake
  • Patent Document 1 discloses a sulfonium salt having a polymerizable unsaturated bond, capable of generating a specific sulfonic acid and a similar iodonium salt.
  • Patent Document 2 discloses a sulfonium salt having a sulfonic acid anion directly attached to the backbone.
  • Patent Documents 3 and 4 disclose resist materials comprising a polymer comprising amino-containing recurring units. Polymeric amines are highly effective for suppressing acid diffusion.
  • Patent Document 5 discloses a resist material based on a polymer comprising recurring units of acid generator and recurring units of amine. It is a single component resist in which both an acid generator function and a quencher function are assigned to a common polymer. However, if the acid diffusion distance is too short, there arises the problem that both dissolution contrast and sensitivity drop.
  • An object of the present invention is to provide a positive resist composition which exhibits a higher sensitivity and resolution than conventional positive resist compositions, low edge roughness (LER, LWR) and small size variation, and forms a pattern of good profile after exposure and development, and a patterning process using the resist composition.
  • LER edge roughness
  • the inventors have found the following.
  • the acid diffusion distance should be minimized. This invites a lowering of sensitivity and a drop of dissolution contrast, raising the problem that the resolution of a two-dimensional pattern such as hole pattern is reduced.
  • the dissolution contrast is increased and at the same time, the acid diffusion distance is minimized. Better results are obtainable using the polymer as a base polymer in a chemically amplified positive resist composition.
  • recurring units having a carboxyl or phenolic hydroxyl group in which the hydrogen is substituted by an acid labile group are incorporated into the base polymer.
  • the invention provides a positive resist composition
  • a positive resist composition comprising a base polymer comprising recurring units having a carboxyl group in which the hydrogen is substituted by a nitrogen-containing tertiary hydrocarbon group.
  • the nitrogen-containing tertiary hydrocarbon group is a nitrogen-containing tertiary cyclic hydrocarbon group.
  • the recurring units have the formula (a).
  • R A is hydrogen or methyl
  • X 1 is each independently a single bond, phenylene, naphthylene, or a C 1 -C 12 linking group containing an ester bond, ether bond or lactone ring
  • R is a nitrogen-containing tertiary hydrocarbon group having the formula (a1) or (a2):
  • R 1 and R 2 are each independently a C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group or C 2 -C 6 alkynyl group, R 1 and R 2 may bond together to form a ring with the carbon atom to which they are attached
  • R 3 and R 5 are each independently hydrogen, a C 1 —C straight, branched or cyclic alkyl group, C 2 -C 10 straight or branched alkoxycarbonyl group, C 3 -C 10 straight or branched alkenyloxycarbonyl group, or C 8 -C 14 aralkyloxycarbonyl group, the group optionally containing an ether bond
  • R 4 is a C 1 -C 6 alkyl group.
  • the base polymer further comprises recurring units having a carboxyl group in which the hydrogen is substituted by an acid labile group and/or recurring units having a phenolic hydroxyl group in which the hydrogen is substituted by an acid labile group. More preferably, the recurring units having a carboxyl group in which the hydrogen is substituted by an acid labile group and the recurring units having a phenolic hydroxyl group in which the hydrogen is substituted by an acid labile group are recurring units having the formula (b1) and recurring units having the formula (b2), respectively.
  • R A is each independently hydrogen or methyl
  • Y 1 is a single bond, phenylene, naphthylene, or a C 1 -C 12 linking group containing an ester bond, ether bond or lactone ring
  • Y 2 is a single bond, ester bond or amide bond
  • R 11 and R 12 each are an acid labile group
  • R 13 is fluorine, trifluoromethyl, cyano or C 1 -C 6 alkyl
  • R 14 is a single bond or a C 1 -C 6 straight or branched alkanediyl group in which some carbon may be replaced by an ether bond or ester bond
  • a is 1 or 2
  • b is an integer of 0 to 4.
  • the base polymer may further comprise recurring units containing an adhesive group selected from the group consisting of hydroxyl, carboxyl, lactone ring, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether bond, ester bond, sulfonic ester bond, cyano, amide, —O—C( ⁇ O)—S—, and —O—C( ⁇ O)—NH—.
  • an adhesive group selected from the group consisting of hydroxyl, carboxyl, lactone ring, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether bond, ester bond, sulfonic ester bond, cyano, amide, —O—C( ⁇ O)—S—, and —O—C( ⁇ O)—NH—.
  • the base polymer may further comprise recurring units of at least one type selected from recurring units having the formulae (d1) to (d3).
  • R A is each independently hydrogen or methyl;
  • Z 1 is a single bond, phenylene, —O—Z 11 —, —C( ⁇ O)—O—Z 11 — or —C( ⁇ O)—NH—Z 11 —
  • Z 11 is a C 1 -C 6 alkanediyl group, C 2 -C 6 alkenediyl group, or phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxyl moiety:
  • Z 2 is a single bond or a C 1 -C 12 divalent group which may contain an ester bond, ether bond or lactone ring;
  • Z 3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—Z 31 —, —C( ⁇ O)—O—Z 31 — or —C(O)—NH—Z 31 —
  • Z 31 is a C 1 -C 6 alkaned
  • the positive resist composition may further comprise an acid generator, organic solvent, quencher, and/or surfactant.
  • the invention provides a pattern forming process comprising the steps of applying the positive resist composition defined above to form a resist film on a substrate, exposing the resist film to high-energy radiation, and developing the exposed resist film in a developer.
  • the high-energy radiation is i-line, KrF excimer laser. ArF excimer laser, EB, or EUV of wavelength 3 to 15 nm.
  • the positive resist composition has a high decomposition efficiency of the acid generator, a remarkable acid diffusion-suppressing effect, a high sensitivity, and a high resolution, and forms a pattern of good profile with improved edge roughness and size variation after exposure and development.
  • the resist composition is fully useful in commercial application and best suited as a micropatterning material for photomasks by EB lithography or for VLSIs by EB or EUV lithography.
  • the resist composition may be used not only in the lithography for forming semiconductor circuits, but also in the formation of mask circuit patterns, micromachines, and thin-film magnetic head circuits.
  • Cn-Cm means a group containing from n to m carbon atoms per group. Me stands for methyl, and Ac for acetyl.
  • One embodiment of the invention is a positive resist composition
  • a positive resist composition comprising a base polymer comprising recurring units having a carboxyl group in which the hydrogen is substituted by a nitrogen-containing tertiary hydrocarbon group.
  • the nitrogen-containing tertiary hydrocarbon group is preferably a nitrogen-containing tertiary cyclic hydrocarbon group because a resist film having a satisfactory acid diffusion-suppressing effect and a high dissolution contrast is obtainable.
  • the recurring units have the formula (a).
  • the recurring units having formula (a) are also referred to as recurring units (a).
  • R A is hydrogen or methyl.
  • X 1 is each independently a single bond, phenylene, naphthylene, or a C 1 -C 12 linking group containing an ester bond, ether bond or lactone ring.
  • R A is as defined above, and R will be defined below.
  • R is a nitrogen-containing tertiary hydrocarbon group having the formula (a1) or (a2).
  • R 1 and R 2 are each independently a C 1 -C 6 alkyl group, C 2 —C alkenyl group or C 2 -C 6 alkynyl group. R and R 2 may bond together to form a ring with the carbon atom to which they are attached.
  • R 3 and R 5 are each independently hydrogen, a C 1 -C 9 straight or branched alkyl group, C 2 -C 10 straight or branched alkoxycarbonyl group, C 3 -C 10 straight or branched alkenyloxycarbonyl group, or C 8 -C 14 aralkyloxycarbonyl group, the group optionally containing an ether bond.
  • R 4 is a C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group or C 2 -C 6 alkynyl group.
  • the circle R a is an alicyclic group of 2 to 10 carbon atoms including the nitrogen atom.
  • the broken line designates a valence bond to the oxygen atom in formula (a).
  • the C 1 -C 6 alkyl group may be straight, branched or cyclic and examples thereof include methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, and cyclohexyl.
  • the C 2 -C 6 alkenyl group may be straight, branched or cyclic and examples thereof include vinyl, 1-propenyl, 2-propenyl, butenyl, hexenyl, and cyclohexenyl.
  • the C 2 -C 6 alkynyl group may be straight, branched or cyclic and examples thereof include ethynyl and butynyl.
  • R 1 and R 2 are preferably methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, vinyl or ethynyl.
  • examples of the straight or branched C 1 -C 9 alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, and n-nonyl.
  • Examples of the straight or branched C 2 -C 10 alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, tert-pentyloxycarbonyl, neopentyloxycarbonyl, and n-hexyloxycarbonyl.
  • Examples of the straight or branched C 3 -C 10 alkenyloxycarbonyl groups include vinyloxycarbonyl and 2-propenyloxycarbonyl.
  • Examples of the C 8 -C 14 alkenyloxycarbonyl groups include benzyloxycarbonyl and phenethyloxycarbonyl.
  • R 3 and R 5 are preferably hydrogen, methyl, ethyl, isopropyl, tert-butyloxycarbonyl, tert-pentyloxycarbonyl, 2-propenyloxycarbonyl or benzyloxycarbonyl.
  • C 1 -C 6 alkyl examples include C 2 -C 6 alkenyl and C 2 -C 6 alkynyl groups represented by R 4 are as exemplified above for R 1 and R 2 .
  • R 4 is preferably methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, vinyl or ethynyl.
  • the recurring unit (a) functions as a quencher due to the inclusion of nitrogen atom.
  • the base polymer may be referred to as a quencher-bound polymer.
  • the quencher-bound polymer has the advantages of a remarkable acid diffusion-suppressing effect and improved resolution.
  • the recurring unit (a) is an acid labile group unit due to the inclusion of a tertiary ester structure. Although an ordinary acid labile group unit follows an acid-aided polarity switch mechanism, the recurring unit (a) has not only the polarity switch function, but also the acid diffusion suppressing function. This enables to enhance dissolution contrast while suppressing acid diffusion.
  • the base polymer may further comprise recurring units having a carboxyl group in which the hydrogen is substituted by an acid labile group, referred to as recurring units (b1), hereinafter, and/or recurring units having a phenolic hydroxyl group in which the hydrogen is substituted by an acid labile group, referred to as recurring units (b2), hereinafter.
  • the preferred recurring units (b1) and (b2) are recurring units having the formulae (b1) and (b2), respectively.
  • R A is each independently hydrogen or methyl.
  • Y 1 is a single bond, phenylene, naphthylene, or a C 1 -C 12 linking group containing an ester bond, ether bond or lactone ring.
  • Y 2 is a single bond, ester bond or amide bond.
  • R 11 and R 12 each are an acid labile group.
  • R 13 is fluorine, trifluoromethyl, cyano or a C 1 -C 6 alkyl group.
  • R 14 is a single bond or a C 1 -C 6 straight or branched alkanediyl group in which some carbon may be replaced by an ether bond or ester bond.
  • the subscript a is 1 or 2
  • b is an integer of 0 to 4.
  • R A and R 12 are as defined above.
  • the acid labile groups represented by R 11 and R 12 may be selected from a variety of such groups, for example, groups of the following formulae (AL-1) to (AL-3).
  • R L10 is a C 4 -C 20 , preferably C 4 -C 5 tertiary hydrocarbon group, a trialkylsilyl group in which each alkyl moiety has 1 to 6 carbon atoms, a C 4 -C 20 alkyl group containing a carbonyl moiety or ester bond, or a group of formula (AL-3).
  • Al is an integer of 0 to 6.
  • the tertiary hydrocarbon group may be branched or cyclic, and examples thereof include tert-butyl, tert-pentyl, 1,1-diethylpropyl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, l-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl, 2-tetrahydropyranyl, and 2-tetrahydrofuranyl.
  • trialkylsilyl group examples include trimethylsilyl, triethylsilyl, and dimethyl-tert-butylsilyl.
  • the alkyl group containing a carbonyl moiety or ester bond may be straight, branched or cyclic, preferably cyclic and examples thereof include 3-oxocyclohexyl, 4-methyl-2-oxooxan-4-yl, and 5-methyl-2-oxooxolan-5-yl.
  • Examples of the acid labile group having formula (AL-1) include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-pentyloxycarbonyl, tert-pentyloxycarbonylmethyl, 1,1-diethylpropyloxycarbonyl, 1,1-diethylpropyloxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentenyloxycabonylmtethyl, 1-ethoxyethoxycarbonyhnlmethyl, 2-tetrahydropyranyloxycarbonyhulmethyl, and 2-tetrahydrofuranyloxycarbonylmethyl.
  • acid labile group having formula (AL-1) examples include groups having the formulae (AL-1)-1 to (AL-1)-10.
  • R L8 is each independently a C 1 -C 10 alkyl group or C 6 -C 20 aryl group.
  • R L9 is hydrogen or a C 1 -C 10 alkyl group.
  • R L10 is a C 2 -C 10 alkyl group or C 6 -C 20 aryl group.
  • the alkyl group may be straight, branched or cyclic.
  • RU and R L2 are each independently hydrogen or a C 1 -C 18 , preferably C 1 -C 10 alkyl group.
  • the alkyl group may be straight, branched or cyclic and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl and n-octyl.
  • R L4 is a C 1 -C 18 , preferably C 1 -C 10 monovalent hydrocarbon group which may contain a heteroatom such as oxygen.
  • the monovalent hydrocarbon group may be straight, branched or cyclic and typical examples thereof include C 1 -C 18 alkyl groups, in which some hydrogen may be substituted by hydroxyl, alkoxy, oxo, amino or alkylamino. Examples of the substituted alkyl group are shown below.
  • a pair of R L2 and R L3 , R L2 and R L4 , or R L3 and R L4 may bond together to form a ring with the carbon atom or carbon and oxygen atoms to which they are attached.
  • a ring-forming combination of R L2 and R L3 , R L2 and R L4 , or R L3 and R L4 is each independently a C 1 -C 18 , preferably C 1 -C 10 straight or branched alkanediyl group.
  • the ring thus formed is preferably of 3 to 10, more preferably 4 to 10 carbon atoms.
  • suitable straight or branched groups include those having formulae (AL-2)-1 to (AL-2)-69, but are not limited thereto.
  • suitable cyclic groups include tetrahydrofuran-2-yl 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl, and 2-methyltetrahydropyran-2-yl.
  • the base polymer may be crosslinked within the molecule or between molecules with these acid labile groups.
  • R L11 and R L12 are each independently hydrogen or a C 1 -C 8 alkyl group which may be straight, branched or cyclic. Also, R L11 and R L12 may bond together to form a ring with the carbon atom to which they are attached, and in this case, R L11 and R L12 are each independently a C 1 -C 8 straight or branched alkanediyl group. R L13 is each independently a C 1 -C 10 alkanediyl group which may be straight, branched or cyclic.
  • B1 and D1 are each independently an integer of 0 to 10, preferably 0 to 5, and C1 is an integer of 1 to 7, preferably 1 to 3.
  • L A is a (C1+1)-valent C 1 -C 50 aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group. In these groups, some carbon may be replaced by a heteroatom-containing moiety, or some carbon-bonded hydrogen may be substituted by a hydroxyl, carboxyl, acyl moiety or fluorine.
  • L A is preferably a C 1 -C 20 alkanediyl, alkanetriyl, alkanetetrayl, or C 6 -C 30 arylene group. The alkanediyl, alkanetriyl, and alkanetetrayl groups may be straight, branched or cyclic.
  • L B is —CO—O—, —NHCO—O— or —NHCONH—.
  • crosslinking acetal groups having formulae (AL-2a) and (AL-2b) include groups having the formulae (AL-2)-70 to (AL-2)-77.
  • R L5 , R L6 and R L7 are each independently a C 1 -C 20 monovalent hydrocarbon group which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine.
  • the monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof include C 1 -C 20 alkyl groups and C 2 -C 20 alkenyl groups.
  • a pair of R L5 and R L6 , R L5 and R L7 , or R L6 and R L7 may bond together to form a C 3 -C 20 aliphatic ring with the carbon atom to which they are attached.
  • Examples of the group having formula (AL-3) include tert-butyl, 1,1-diethylpropyl, 1-ethylnorbornyl, 1-methylcyclopentyl, 1-isopropylcyclopentyl, 1-ethycyclopentyl, l-methylcyclohexyl 2-(2-methyl)adamantyl, 2-(2-ethyl)adamantyl, and tert-pentyl.
  • Examples of the group having formula (AL-3) also include groups having the formulae (AL-3)-1 to (AL-3)-18.
  • R L14 is each independently a C 1 -C 8 alkyl group or C 6 -C 20 aryl group.
  • R L15 and R L17 are each independently hydrogen or a C 1 -C 20 alkyl group.
  • R L16 is a C 6 -C 20 aryl group.
  • the alkyl group may be straight, branched or cyclic. Typical of the aryl group is phenyl.
  • the base polymer may be crosslinked within the molecule or between molecules with these acid labile groups.
  • R L14 is as defined above.
  • R L18 is a (E1+1)-valent C 1 -C 20 alkanediyl group or (E1+1)-valent C 6 -C 20 arylene group, which may contain a heteroatom such as oxygen, sulfur or nitrogen.
  • the alkanediyl group may be straight, branched or cyclic.
  • E1 is an integer of 1 to 3.
  • Examples of the monomer from which recurring units containing an acid labile group of formula (AL-3) are derived include (meth)acrylates having an exo-form structure represented by the formula (AL-3)-21.
  • R A is as defined above.
  • R Lc1 is a C 1 -C 5 alkyl group or an optionally substituted C 6 -C 20 aryl group; the alkyl group may be straight, branched or cyclic.
  • R Lc2 to R Lc11 are each independently hydrogen or a C 1 -C 15 monovalent hydrocarbon group which may contain a heteroatom; oxygen is a typical heteroatom.
  • Suitable monovalent hydrocarbon groups include C 1 -C 15 alkyl groups and C 6 -C 15 aryl groups.
  • a pair of R Lc2 and R Lc3 , R Lc4 and R Lc6 , R Lc4 and R Lc7 , R Lc5 and R Lc7 , R Lc5 and R Lc11 , R Lc6 and R Lc10 , R Lc8 and R Lc9 , or R Lc9 and R Lc10 , taken together, may form a ring with the carbon atom to which they are attached, and in this event, the ring-forming combination is a C 1 -C 15 divalent hydrocarbon group which may contain a heteroatom.
  • R Lc2 and R Lc11 , R Lc8 and R Lc11 , or R Lc4 and R Lc6 which are attached to vicinal carbon atoms may bond together directly to form a double bond.
  • the formula also represents an enantiomer.
  • recurring units having an acid labile group of formula (AL-3) are recurring units of (meth)acrylate having a furandiyl, tetrahydrofurandiyl or oxanorbornauediyl group as represented by the following formula (AL-3)-22.
  • R A is as defined above.
  • R Lc12 and R Lc13 are each independently a C 1 -C 10 monovalent hydrocarbon group, or R Lc12 and R Lc13 , taken together, may form an aliphatic ring with the carbon atom to which they are attached.
  • R Lc14 is furandiyl, tetrahydrofurandiyl or oxanorbornanediyl.
  • R Lc15 is hydrogen or a C 1 -C 10 monovalent hydrocarbon group which may contain a heteroatom.
  • the monovalent hydrocarbon group may be straight, branched or cyclic, and examples thereof include C 1 -C 10 alkyl groups.
  • recurring units (c) having an adhesive group may be incorporated.
  • the adhesive group is selected from hydroxyl, carboxyl, lactone ring, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether, ester, sulfonic acid ester, cyano, amide, —O—C( ⁇ O)—S— and —O—C( ⁇ O)—NH—.
  • R A is as defined above.
  • recurring units (d) derived from an onium salt having a polymerizable unsaturated bond may be incorporated in the base polymer.
  • the preferred recurring units (d) are recurring units having the following formulae (d1), (d2) and (d3). These units are simply referred to as recurring units (d1), (d2) and (d3), which may be used alone or in combination of two or more types.
  • R A is each independently hydrogen or methyl.
  • Z 1 is a single bond, phenylene. —O—Z 11 —, —C( ⁇ O)—O—Z 11 — or —C( ⁇ O)—NH—Z 11 —, wherein Z 11 is a C 1 -C 6 alkanediyl group, C 2 -C 6 alkenediyl group, or phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxyl moiety.
  • Z 2 is a single bond or a C 1 -C 12 divalent group which may contain an ester bond, ether bond or lactone ring.
  • Z 3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—Z 31 —, —C( ⁇ O)—O—Z 31 — or —C( ⁇ O)—NH—Z 31 —, wherein Z 31 is a C 1 -C 6 alkanediyl group, C 2 —C alkenediyl group, or phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxyl moiety.
  • Rf 1 to Rf 4 are each independently hydrogen, fluorine or trifluoromethyl, at least one of Rf 1 to Rf 4 being fluorine.
  • at least one of Rf 3 and Rf 4 is fluorine, most preferably both Rf 3 and Rf 4 are fluorine.
  • R 21 to R 22 are each independently a C 1 -C 20 monovalent hydrocarbon group which may contain a heteroatom, any two of R 23 , R 24 and R 25 or any two of R 26 , R 27 and R 28 may bond together to form a ring with the sulfur atom to which they are attached.
  • the monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof include C 1 -C 12 alkyl, C 6 -C 12 aryl, and C 7 -C 20 aralkyl groups.
  • some or all hydrogen may be substituted by C 1 -C 10 alkyl, halogen, trifluoromethyl, cyano, nitro, hydroxyl mercapto, C 1 -C 10 alkoxy, C 2 -C 10 alkoxycarbonyl, or C 2 -C 10 acyloxy moiety, or some carbon may be replaced by a carbonyl moiety, ether bond or ester bond.
  • M ⁇ is a non-nucleophilic counter ion.
  • the non-nucleophilic counter ion include halide ions such as chloride and bromide ions; fluoroalkylsulfonate ions such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; arylsulfonate ions such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkylsulfonate ions such as mesylate and butanesulfonate: imide ions such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide and bis(perfluorobutylsulfonyl)imide; meth
  • sulfonate ions having fluorine substituted at ⁇ -position as represented by the formula (K-1) and sulfonate ions having fluorine substituted at ⁇ -position and trifluoromethyl at ⁇ -position as represented by the formula (K-2).
  • R 31 is hydrogen, or a C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, or C 6 -C 20 aryl group, which may contain an ether bond, ester bond, carbonyl moiety, lactone ring, or fluorine atom.
  • the alkyl and alkenyl groups may be straight, branched or cyclic.
  • R 32 is hydrogen, or a C 1 -C 30 alkyl group, C 2 -C 30 acyl group, C 2 -C 20 alkenyl group, C 6 -C 20 aryl group or C 6 -C 20 aryloxy group, which may contain an ether bond, ester bond, carbonyl moiety or lactone ring.
  • the alkyl, acyl and alkenyl groups may be straight, branched or cyclic.
  • Examples of the monomer from which recurring unit (d1) is derived are shown below, but not limited thereto.
  • R A and M ⁇ are as defined above.
  • R A is as defined above.
  • R A is as defined above.
  • Recurring units (d1) to (d3) have the function of acid generator.
  • the attachment of an acid generator to the polymer main chain is effective in restraining acid diffusion, thereby preventing a reduction of resolution due to blur by acid diffusion. Also LWR is improved since the acid generator is uniformly distributed.
  • an acid generator of addition type (to be described later) may be omitted.
  • recurring units (e) may be incorporated in the base polymer, examples of which include styrene, acenaphthylene, indene, coumarin, and coumarone.
  • a fraction of these units is: preferably 0 ⁇ a ⁇ 1.0, 0 ⁇ b1 ⁇ 0.9, 0 ⁇ b2 ⁇ 0.9, 0 ⁇ b1+b2 ⁇ 0.9, 0 ⁇ c ⁇ 0.9, 0 ⁇ d1 ⁇ 0.5, 0 ⁇ d2 ⁇ 0.5, 0 ⁇ d3 ⁇ 0.5, 0 ⁇ d1+d2+d3 ⁇ 0.5, and 0 ⁇ e ⁇ 0.5;
  • the base polymer may be synthesized by any desired methods, for example, by dissolving one or more monomers selected from the monomers corresponding to the foregoing recurring units in an organic solvent, adding a radical polymerization initiator thereto, and heating for polymerization.
  • organic solvent which can be used for polymerization include toluene, benzene, tetrahydrofuran (THF), diethyl ether, and dioxane.
  • polymerization initiator examples include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide.
  • AIBN 2,2′-azobisisobutyronitrile
  • 2,2′-azobis(2,4-dimethylvaleronitrile) dimethyl 2,2-azobis(2-methylpropionate
  • benzoyl peroxide and lauroyl peroxide.
  • reaction temperature is 50 to 80° C.
  • reaction time is 2 to 100 hours, more preferably 5 to 20 hours.
  • the hydroxyl group may be replaced by an acetal group susceptible to deprotection with acid, typically ethoxyethoxy, prior to polymerization, and the polymerization be followed by deprotection with weak acid and water.
  • the hydroxyl group may be replaced by an acetyl, formyl, pivaloyl or similar group prior to polymerization, and the polymerization be followed by alkaline hydrolysis.
  • hydroxystyrene or hydroxyvinylnaphthalene is copolymerized
  • an alternative method is possible. Specifically, acetoxystyrene or acetoxyvinylnaphthalene is used instead of hydroxystyrene or hydroxyvinylnaphthalene, and after polymerization, the acetoxy group is deprotected by alkaline hydrolysis, for thereby converting the polymer product to hydroxystyrene or hydroxyvinylnaphthalene.
  • a base such as aqueous ammonia or triethylamine may be used.
  • the reaction temperature is ⁇ 20° C. to 100° C., more preferably 0° C. to 60° C.
  • the reaction time is 0.2 to 100 hours, more preferably 0.5 to 20 hours.
  • the base polymer should preferably have a weight average molecular weight (Mw) in the range of 1,000 to 500,000, and more preferably 2,000 to 30,000, as measured by GPC versus polystyrene standards using tetrahydrofuran (THF) solvent. With too low a Mw, the resist composition may become less heat resistant. A polymer with too high a Mw may lose alkaline solubility and give rise to a footing phenomenon after pattern formation.
  • Mw weight average molecular weight
  • the base polymer should preferably have a narrow dispersity (Mw/Mn) of 1.0 to 2.0, especially 1.0 to 1.5, in order to provide a resist composition suitable for micropatterning to a small feature size.
  • the base polymer may be a blend of two or more polymers which differ in compositional ratio, Mw or Mw/Mn. It may also be a blend of a polymer comprising recurring units (a) and a polymer comprising recurring units (b1) and/or (b2), but not recurring units (a).
  • the positive resist composition may contain an acid generator capable of generating a strong acid, also referred to as acid generator of addition type.
  • the “strong acid” is a compound having a sufficient acidity to induce deprotection reaction of acid labile groups on the base polymer.
  • the acid generator is typically a compound (PAG) capable of generating an acid upon exposure to actinic ray or radiation.
  • PAG used herein may be any compound capable of generating an acid upon exposure to high-energy radiation, those compounds capable of generating sulfonic acid, imidic acid (imide acid) or methide acid are preferred.
  • Suitable PAGs include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate acid generators.
  • Suitable PAGs are as exemplified in U.S. Pat. No. 7,537,880 (JP-A 2008-111103, paragraphs [0122]-[0142]).
  • sulfonium salts having the formula (1-1) and iodonium salts having the formula (1-2) are useful PAGs.
  • R 101 to R 105 are each independently a C 1 -C 2 monovalent hydrocarbon group which may contain a heteroatom. Any two of R 101 , R 102 and R 103 may bond together to form a ring with the sulfur atom to which they are attached.
  • the monovalent hydrocarbon group may be straight, branched or cyclic, and examples thereof are as exemplified above for R 21 to R 28 in formulae (d1) to (d3).
  • X is an anion selected from the formulae (1A) to (1D).
  • R fa is fluorine or a C 1 -C 40 monovalent hydrocarbon group which may contain a heteroatom.
  • the monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof are as will be exemplified below for R 107 .
  • R 106 is hydrogen or trifluoromethyl, preferably trifluoromethyl.
  • R 107 is a C 1 -C 3 monovalent hydrocarbon group which may contain a heteroatom. Suitable heteroatoms include oxygen, nitrogen, sulfur and halogen, with oxygen being preferred. Of the monovalent hydrocarbon groups, those of 6 to 30 carbon atoms are preferred because a high resolution is available in fine pattern formation.
  • the monovalent hydrocarbon group may be straight, branched or cyclic. Examples thereof include straight or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, icosanyl; monovalent saturated alicyclic hydrocarbon groups such as 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecanyl, tetracyclododecanylmethyl, dicyclohexylmethyl; monovalent
  • heteroatom-containing monovalent hydrocarbon groups are tetrahydrofuryl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl.
  • R fb1 and R fb2 are each independently fluorine or a C 1 -C 40 monovalent hydrocarbon group which may contain a heteroatom.
  • the monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof are as exemplified above for R 107 .
  • R fb1 and R fb2 each are fluorine or a straight C 1 -C 4 fluorinated alkyl group.
  • a pair of R fb1 and R fb2 may bond together to form a ring with the linkage (—CF 2 —SO 2 —N ⁇ —SO 2 —CF 2 —) to which they are attached, and preferably the pair is a fluorinated ethylene or fluorinated propylene group.
  • R fc2 and R fc3 are each independently fluorine or a C 1 -C 40 monovalent hydrocarbon group which may contain a heteroatom.
  • the monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof are as exemplified above for R 107 .
  • R fc1 , R fc2 and R fc3 each are fluorine or a straight C 1 -C 4 fluorinated alkyl group.
  • a pair of R fc1 and R fc2 may bond together to form a ring with the linkage (—CF 2 —SO 2 —C ⁇ —SO 2 —CF 2 —) to which they are attached, and preferably the pair is a fluorinated ethylene or fluorinated propylene group.
  • R fd is a C 1 -C 40 monovalent hydrocarbon group which may contain a heteroatom.
  • the monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof are as exemplified above for R 107 .
  • the compound having the anion of formula (1D) has a sufficient acid strength to cleave acid labile groups in the base polymer because it is free of fluorine at ⁇ -position of sulfo group, but has two trifluoromethyl groups at 3-position. Thus the compound is a useful PAG.
  • a compound having the formula (2) is also a useful PAG.
  • R 201 and R 202 are each independently a C 1 -C 30 monovalent hydrocarbon group which may contain a heteroatom.
  • R 203 is a C 1 -C 30 divalent hydrocarbon group which may contain a heteroatom. Any two of R 201 , R 202 and R 203 may bond together to form a ring with the sulfur atom to which they are attached.
  • L is a single bond, ether bond or a C 1 -C 20 divalent hydrocarbon group which may contain a heteroatom.
  • X A , X B , X C and X D are each independently hydrogen, fluorine or trifluoromethyl, with the proviso that at least one of X A , X B , X C and X D is fluorine or trifluoromethyl, and k is an integer of 0 to 3.
  • the monovalent hydrocarbon group may be straight, branched or cyclic. Examples thereof include straight or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, 2-ethylhexyl; monovalent saturated cyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbormyl, oxanorbornyl, tricyclo[5.2.1.0 2,6 ]decanyl, adamantyl;
  • the divalent hydrocarbon group may be straight, branched or cyclic. Examples thereof include straight or branched alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl; divalent saturated cyclic hydrocarbon groups
  • the foregoing groups in which some hydrogen is substituted by an alkyl group such as methyl, ethyl, propyl, n-butyl or tert-butyl, or in which some hydrogen is substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or in which some carbon is replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxyl, cyano, carbonyl, ether bond, ester bond, sulfonic acid ester bond, carbonate, lactone ring, sultone ring, carboxylic acid anhydride or haloalkyl moiety.
  • the preferred heteroatom is oxygen.
  • L is as defined above.
  • “A” is hydrogen or trifluoromethyl, preferably trifluoromethyl.
  • R 301 , R 302 and R 303 are each independently hydrogen or a C 1 -C 20 monovalent hydrocarbon group which may contain a heteroatom.
  • the monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof are as exemplified above for R 107 .
  • the subscripts x and y each are an integer of 0 to 5, and z is an integer of 0 to 4.
  • those compounds having an anion of formula (1A′) or (1D) are especially preferred because of reduced acid diffusion and high solubility in resist solvent, and those compounds having an anion of formula (2′) are especially preferred because of minimized acid diffusion.
  • sulfonium and iodonium salts having an anion containing an iodized or brominated aromatic ring are useful PAGs. These salts typically have the formulae (3-1) and (3-2).
  • X is iodine or bromine.
  • groups X may be identical or different.
  • L 1 is a single bond, ether bond, ester bond, or a C 1 -C 6 alkanediyl group which may contain an ether bond or ester bond.
  • the alkanediyl group may be straight, branched or cyclic.
  • R 401 is hydroxyl, carboxyl, fluorine, chlorine, bromine, amino or a C 1 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 2 -C 10 alkoxycarbonyl, C 2 -C 20 acyloxy group, or C 1 -C 20 alkylsulfonyloxy group, which may contain fluorine, chlorine, bromine, hydroxyl, amino or C 1 -C 10 alkoxy moiety, or —NR 401A —C( ⁇ O)—R 401B or —NR 401A —C( ⁇ O)—O—R 401B .
  • R 401A is hydrogen or a C 1 -C 6 alkyl group which may contain halogen, hydroxyl, C 1 -C 6 alkoxy, C 2 -C 6 acyl or C 2 -C 6 acyloxy moiety
  • R 401B is a C 1 -C 16 alkyl group, C 2 -C 16 alkenyl group or C 6 -C 12 aryl group, which may contain halogen, hydroxyl, a C 1 -C 6 alkoxy, C 2 -C 6 acyl or C 2 -C 6 acyloxy moiety.
  • the alkyl, alkoxy, alkoxycarbonyl, acyloxy, acyl and alkenyl groups may be straight, branched or cyclic. When t is at least 2, groups R 401 may be identical or different.
  • R 401 is preferably selected from hydroxyl —NR 401A —C( ⁇ O)—R 401B , —NR 401A —C( ⁇ O)—R 401B , fluorine, chlorine, bromine, methyl, and methoxy.
  • the linking group may contain oxygen, sulfur or nitrogen.
  • Rf 11 to Rf 14 are each independently hydrogen, fluorine or trifluaromethyl, at least one thereof being fluorine or trifluoromethyl. Also Rf 11 and Rf 12 , taken together, may form a carbonyl group. Most preferably both Rf 13 and Rf 14 are fluorine.
  • R 403 , R 404 , R 405 , R 406 and R 407 are each independently a C 1 -C 20 monovalent hydrocarbon group which may contain a heteroatom. Any two of R 403 , R 404 and R 405 may bond together to form a ring with the sulfur atom to which they are attached.
  • the monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof include C 1 -C 12 alkyl groups, C 2 -C 12 alkenyl groups, C 2 -C 12 alkynyl groups, C 6 -C 20 aryl groups, and C 1 -C 12 aralkyl groups.
  • some or all hydrogen may be substituted by hydroxyl, carboxyl, halogen, cyano, amide, nitro, mercapto, sultone, sulfone, or sulfonium salt-containing moiety; or some carbon may be replaced by an ether bond, ester bond, carbonyl, carbonate or sulfonic acid ester bond.
  • the subscript r is an integer of 1 to 3.
  • the subscript s is an integer of 1 to 5, and t is an integer of 0 to 3, meeting 1 ⁇ s+t ⁇ 5.
  • s is an integer of 1 to 3, more preferably 2 or 3, and t is an integer of 0 to 2.
  • the cation moiety in the sulfonium salt having formula (3-1) is as exemplified above for the cation moiety in the sulfonium salt having formula (1-1).
  • the cation moiety in the iodonium salt having formula (3-2) is as exemplified above for the cation moiety in the iodonium salt having formula (1-2).
  • the acid generator of addition type is preferably used in an amount of 0.1 to 50 parts, more preferably 1 to 40 parts by weight per 100 parts by weight of the base polymer.
  • the positive resist composition functions as a chemically amplified positive resist composition.
  • the positive resist composition may contain an organic solvent.
  • the organic solvent is not particularly limited as long as the foregoing components and other components are dissolvable therein. Examples of the organic solvent used herein are described in U.S. Pat. No. 7,537,880 (JP-A 2008-111103, paragraphs [0144]-[0145]).
  • Exemplary solvents include ketones such as cyclohexanone, cyclopentanone and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, l-ethoxy-2-propanol, and diacetone alcohol (DAA); ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-
  • the organic solvent is preferably added in an amount of 100 to 10,000 parts, and more preferably 200 to 8,000 parts by weight per 100 parts by weight of the base polymer.
  • a quencher may be blended.
  • the quencher is typically selected from conventional basic compounds.
  • Conventional basic compounds include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds with carboxyl group, nitrogen-containing compounds with sulfonyl group, nitrogen-containing compounds with hydroxyl group, nitrogen-containing compounds with hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and carbamate derivatives.
  • primary, secondary, and tertiary amine compounds specifically amine compounds having a hydroxyl, ether bond, ester bond, lactone ring, cyano, or sulfonic acid ester bond as described in JP-A 2008-111103, paragraphs [0146]-[0164], and compounds having a carbamate group as described in JP 3790649.
  • Addition of a basic compound may be effective for further suppressing the diffusion rate of acid in the resist film or correcting the pattern profile.
  • Suitable quenchers also include onium salts such as sulfonium salts, iodonium salts and ammonium salts of sulfonic acids which are not fluorinated at ⁇ -position and similar onium salts of carboxylic acid, as described in JP-A 2008-158339. While an ⁇ -fluorinated sulfonic acid, imide acid, and methide acid are necessary to deprotect the acid labile group of carboxylic acid ester, an ⁇ -non-fluorinated sulfonic acid or a carboxylic acid is released by salt exchange with an ⁇ -non-fluorinated onium salt. An ⁇ -non-fluorinated sulfonic acid and a carboxylic acid function as a quencher because they do not induce deprotection reaction.
  • onium salts such as sulfonium salts, iodonium salts and ammonium salts of sulfonic acids which are not fluorinated at
  • quenchers of polymer type as described in U.S. Pat. No. 7,598,016 (JP-A 2008-239918).
  • the polymeric quencher segregates at the resist surface after coating and thus enhances the rectangularity of resist pattern.
  • the polymeric quencher is also effective for preventing a film thickness loss of resist pattern or rounding of pattern top.
  • the quencher is preferably added in an amount of 0 to 5 parts, more preferably 0 to 4 parts by weight per 100 parts by weight of the base polymer.
  • the quenchers may be used alone or in admixture.
  • ком ⁇ онент such as surfactant and dissolution inhibitor may be blended in any desired combination to formulate a positive resist composition.
  • This positive resist composition has a very high sensitivity in that the dissolution rate in developer of the base polymer in exposed areas is accelerated by catalytic reaction.
  • the resist film has a high dissolution contrast, resolution, exposure latitude, and process adaptability, and provides a good pattern profile after exposure, and minimal proximity bias because of restrained acid diffusion.
  • Exemplary surfactants are described in JP-A 2008-111103, paragraphs [0165]-[0166]. Inclusion of a surfactant may improve or control the coating characteristics of the resist composition.
  • the surfactant may be used alone or in admixture.
  • the surfactant is preferably added in an amount of 0.0001 to 10 parts by weight per 100 parts by weight of the base polymer.
  • a dissolution inhibitor may lead to an increased difference in dissolution rate between exposed and unexposed areas and a further improvement in resolution.
  • the dissolution inhibitor which can be used herein is a compound having at least two phenolic hydroxyl groups on the molecule, in which an average of from 0 to 100 mol % of all the hydrogen atoms on the phenolic hydroxyl groups are replaced by acid labile groups or a compound having at least one carboxyl group on the molecule, in which an average of 50 to 100 mol % of all the hydrogen atoms on the carboxyl groups are replaced by acid labile groups, both the compounds having a molecular weight of 100 to 1,000, and preferably 150 to 800.
  • Typical are bisphenol A, trisphenol, phenolphthalein, cresol novolac, naphthalenecarboxylic acid, adamantanecarboxylic acid, and cholic acid derivatives in which the hydrogen atom on the hydroxyl or carboxyl group is replaced by an acid labile group, as described in U.S. Pat. No. 7,771,914 (JP-A 2008-122932, paragraphs [0155]-[0178]).
  • the dissolution inhibitor is preferably added in an amount of 0 to 50 parts, more preferably 5 to 40 parts by weight per 100 parts by weight of the base polymer.
  • a polymeric additive (or water repellency improver) may also be added for improving the water repellency on surface of a resist film as spin coated.
  • the water repellency improver may be used in the topcoatless immersion lithography.
  • Suitable water repellency improvers include polymers having a fluoroalkyl group and polymers having a specific structure with a 1,1,1,3,3,3-hexafluoro-2-propanol residue and are described in JP-A 2007-297590 and JP-A 2008-111103, for example.
  • the water repellency improver to be added to the resist composition should be soluble in the organic solvent as the developer.
  • the water repellency improver of specific structure with a 1,1,1,3,3,3-hexafluoro-2-propanol residue is well soluble in the developer.
  • a polymer having an amino group or amine salt copolymerized as recurring units may serve as the water repellent additive and is effective for preventing evaporation of acid during PEB, thus preventing any hole pattern opening failure after development.
  • An appropriate amount of the water repellency improver is 0 to 20 parts, preferably 0.5 to 10 parts by weight per 100 parts by weight of the base polymer.
  • an acetylene alcohol may be blended in the resist composition. Suitable acetylene alcohols are described in JP-A 2008-122932, paragraphs [0179]-[0182]. An appropriate amount of the acetylene alcohol blended is 0 to 5 parts by weight per 100 parts by weight of the base polymer.
  • the positive resist composition is used in the fabrication of various integrated circuits. Pattern formation using the resist composition may be performed by well-known lithography processes. The process generally involves coating, exposure, and development. If necessary, any additional steps may be added.
  • the positive resist composition is first applied onto a substrate on which an integrated circuit is to be formed (e.g., Si. SiO 2 , SiN, SiON, TiN, WSi, BPSG, SOG, or organic antireflective coating) or a substrate on which a mask circuit is to be formed (e.g., Cr, CrO, CrON, MoSi 2 , or SiO 2 ) by a suitable coating technique such as spin coating, roll coating, flow coating, dipping, spraying or doctor coating.
  • the coating is prebaked on a hotplate at a temperature of 60 to 150° C. for 10 seconds to 30 minutes, preferably at 80 to 120° C. for 30 seconds to 20 minutes.
  • the resulting resist film is generally 0.01 to 2 ⁇ m thick.
  • the resist film is then exposed to a desired pattern of high-energy radiation such as UV, deep-UV, EB, EUV of wavelength 3 to 15 nm, x-ray, soft x-ray, excimer laser light, ⁇ -ray or synchrotron radiation.
  • high-energy radiation such as UV, deep-UV, EUV, x-ray, soft x-ray, excimer laser light, ⁇ -ray or synchrotron radiation.
  • the resist film is exposed thereto through a mask having a desired pattern in a dose of preferably about 1 to 200 mJ/cm 2 , more preferably about 10 to 100 mJ/cm 2 .
  • the resist film is exposed thereto through a mask having a desired pattern or directly in a dose of preferably about 0.1 to 100 ⁇ C/cm 2 , more preferably about 0.5 to 50 ⁇ C/cm 2 .
  • inventive resist composition is suited in micropatterning using KrF excimer laser, ArF excimer laser, EB, EUV, x-ray, soft x-ray, ⁇ -ray or synchrotron radiation, especially in micropatterning using EB or EUV.
  • the resist film may be baked (PEB) on a hot plate at 60 to 150° C. for 10 seconds to 30 minutes, preferably at 80 to 120° C. for 30 seconds to 20 minutes.
  • PEB baked
  • the resist film is developed in a developer in the form of an aqueous base solution for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes by conventional techniques such as dip, puddle and spray techniques.
  • a typical developer is a 0.1 to 10 wt %, preferably 2 to 5 wt % aqueous solution of tetramnethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), or tetrabutylammonium hydroxide (TBAH).
  • TMAH tetramnethylammonium hydroxide
  • TEAH tetraethylammonium hydroxide
  • TPAH tetrapropylammonium hydroxide
  • TBAH tetrabutylammonium hydroxide
  • a negative pattern may be formed via organic solvent development using a positive resist composition comprising a base polymer having an acid labile group.
  • the developer used herein is preferably selected from among 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethy
  • the resist film is rinsed.
  • a solvent which is miscible with the developer and does not dissolve the resist film is preferred.
  • Suitable solvents include alcohols of 3 to 10 carbon atoms, ether compounds of 8 to 12 carbon atoms, alkanes, alkenes, and alkynes of 6 to 12 carbon atoms, and aromatic solvents.
  • suitable alcohols of 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-2
  • Suitable ether compounds of 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-s-butyl ether, di-n-pentyl ether, diisopentyl ether, di-s-pentyl ether, di-t-pentyl ether, and di-n-hexyl ether.
  • Suitable alkanes of 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane.
  • Suitable alkenes of 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene.
  • Suitable alkynes of 6 to 12 carbon atoms include hexyne, heptyne, and octyne.
  • Suitable aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, t-butylbenzene and mesitylene.
  • Rinsing is effective for minimizing the risks of resist pattern collapse and defect formation. However, rinsing is not essential. If rinsing is omitted, the amount of solvent used may be reduced.
  • a hole or trench pattern after development may be shrunk by the thermal flow, RELACS® or DSA process.
  • a hole pattern is shrunk by coating a shrink agent thereto, and baking such that the shrink agent may undergo crosslinking at the resist surface as a result of the acid catalyst diffusing from the resist layer during bake, and the shrink agent may attach to the sidewall of the hole pattern.
  • the bake is preferably at a temperature of 70 to 180° C., more preferably 80 to 170° C., for a time of 10 to 300 seconds. The extra shrink agent is stripped and the hole pattern is shrunk.
  • Mw and Mw/Mn are determined by GPC versus polystyrene standards using THF solvent.
  • Monomer 2 of the following formula was obtained by the same procedure as in Synthesis Example 1-1 aside from using 14.3 g of 2-(4-piperidyl)-2-propanol instead of 2-azetidin-3-yl-propan-2-ol.
  • Monomer 3 of the following formula was obtained by the same procedure as in Synthesis Example 1-1 aside from using 12.9 g of 1,4-dimethyl-4-piperidinol instead of 2-azetidin-3-yl-propen-2-ol.
  • Monomer 4 of the following formula was obtained by the same procedure as in Synthesis Example 1-1 aside from using 13.9 g of 4-ethynyl-1-methyl-4-piperidinol instead of 2-azetidin-3-yl-propan-2-ol.
  • Monomer 5 of the following formula was obtained by the same procedure as in Synthesis Example 1-1 aside from using 11.5 g of 3-methylpiperidin-3-ol instead of 2-azetidin-3-yl-propan-2-ol.
  • Monomer 6 of the following formula was obtained by the same procedure as in Synthesis Example 1-1 aside from using 24.3 g of 2-(4-tert-butoxycarbonylpiperidyl)-2-propanol instead of 2-azetidin-3-yl-propau-2-ol.
  • PAG Monomers 1 to 3 identified below were used in the synthesis of polymers.
  • a 2-L flask was charged with 1.9 g of Monomer 3, 5.2 g of 1-(cyclopropyl-1-yl)-1-methylethyl methacrylate, 3.5 g of 3-fluoro-4-(methylcyclohexyloxy)styrene, 4.8 g of 3-hydroxystyrene, 11.2 g of PAG Monomer 3, and 40 g of THF as solvent.
  • the reactor was cooled at ⁇ 70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times.
  • the reactor was warmed up to room temperature, whereupon 1.2 g of AIBN was added.
  • the reactor was heated at 60° C., whereupon reaction ran for 15 hours.
  • Comparative Polymer 1 was obtained by the same procedure as in Synthesis Example 2-1 except that Monomer 1 was omitted. Comparative Polymer 1 was analyzed for composition by 13 C- and 1 H-NMR and for Mw and Mw/Mn by GPC.
  • Comparative Polymer 2 was obtained by the same procedure as in Synthesis Example 2-1 except that 2-(dimethylamino)ethyl methacrylate was used instead of Monomer 1. Comparative Polymer 2 was analyzed for composition by 13 C- and 1 H-NMR and for Mw and Mw/Mn by GPC.
  • Comparative Polymer 3 was obtained by the same procedure as in Synthesis Example 2-4 except that Monomer 4 was omitted. Comparative Polymer 3 was analyzed for composition by 13 C- and 1 H-NMR and for Mw and Mw/Mn by GPC.
  • Positive resist compositions were prepared by dissolving components in a solvent in accordance with the recipe shown in Table 1, and filtering through a filter having a pore size of 0.2 ⁇ m.
  • the solvent contained 100 ppm of surfactant FC-4430 (3M).
  • FC-4430 3M
  • the components in Table 1 are as identified below.
  • Each of the resist compositions in Table 1 was spin coated on a silicon substrate having a 20-nm coating of silicon-containing spin-on hard mask SHB-A940 (Shin-Etsu Chemical Co., Ltd., Si content 43 wt %) and prebaked on a hotplate at 105° C. for 60 seconds to form a resist film of 60 nm thick.
  • SHB-A940 Silicon-containing spin-on hard mask
  • the resist film was exposed to EUV through a mask bearing a hole pattern at a pitch 46 nm (on-wafer size) and +20% bias.
  • the resist film was baked (PEB) on a hotplate at the temperature shown in Table 1 for 60 seconds and developed in a 2.38 wt % TMAH aqueous solution for 30 seconds to form a hole pattern having a size of 23 nm.
  • the resist pattern was observed under CD-SEM (CG-5000, Hitachi High-Tedmologies Corp.). The exposure dose that provides a hole pattern having a size of 23 nm is reported as sensitivity. The size of 50 holes was measured, from which a size variation (3c) was computed and reported as CDU.
  • the resist composition is shown in Table 1 together with the sensitivity and CDU of EUV lithography.

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Abstract

A positive resist composition comprising a base polymer comprising recurring units having a nitrogen-containing tertiary ester structure exhibits a high sensitivity, high resolution, low edge roughness (LER, LWR) and small size variation, and forms a pattern of good profile after exposure and development.

Description

CROSS-REFERENCE TO RELATED APPLICATION
This non-provisional application claims priority under 35 U.S.C. § 119(a) on Patent Application No. 2018-234513 filed in Japan on Dec. 14, 2018, the entire contents of which are hereby incorporated by reference.
TECHNICAL FIELD
This invention relates to a positive resist composition and a patterning process using the composition.
BACKGROUND ART
To meet the demand for higher integration density and operating speed of LSIs, the effort to reduce the pattern rule is in rapid progress. The wide-spreading flash memory market and the demand for increased storage capacities drive forward the miniaturization technology. As the advanced miniaturization technology, manufacturing of microelectronic devices at the 10-nm node by the immersion ArF lithography has been implemented in a mass scale. The candidates for the next generation 7-nm node devices and next-but-one generation 5-nm node devices include extreme ultraviolet (EUV) lithography of wavelength 13.5 an and double patterning version of the ArF lithography, on which active research efforts have been made.
The exposure system for mask manufacturing made a transition from the laser beam exposure system to the EB exposure system to increase the accuracy of line width. Since a further size reduction became possible by increasing the accelerating voltage of the electron gun in the EB exposure system, the accelerating voltage increased from 10 kV to 30 kV and reached 50 kV in the current mainstream system, with a voltage of 100 kV being under investigation.
As the accelerating voltage increases, a lowering of sensitivity of resist film becomes of concern. As the accelerating voltage increases, the influence of forward scattering in a resist film becomes so reduced that the contrast of electron image writing energy is improved to ameliorate resolution and dimensional control whereas electrons can pass straightforward through the resist film so that the resist film becomes less sensitive. Since the mask exposure tool is designed for exposure by direct continuous writing, a lowering of sensitivity of resist film leads to an undesirably reduced throughput. Due to a need for higher sensitivity, chemically amplified resist compositions are studied.
As the feature size reduces, image blurs due to acid diffusion become a problem. To insure resolution for fine patterns with a size of 45 nm et seq., not only an improvement in dissolution contrast is important as previously reported, but control of acid diffusion is also important as reported in Non-Patent Document 1. Since chemically amplified resist compositions are designed such that sensitivity and contrast are enhanced by acid diffusion, an attempt to minimize acid diffusion by reducing the temperature and/or time of post-exposure bake (PEB) fails, resulting in drastic reductions of sensitivity and contrast.
A triangular tradeoff relationship among sensitivity, resolution, and edge roughness has been pointed out. Specifically, a resolution improvement requires to suppress acid diffusion whereas a short acid diffusion distance leads to a loss of sensitivity.
The addition of an acid generator capable of generating a bulky acid is an effective means for suppressing acid diffusion. It was then proposed to incorporate in a polymer recurring units derived from an onium salt having a polymerizable unsaturated bond. Since this polymer functions as an acid generator, it is referred to as polymer-bound acid generator. Patent Document 1 discloses a sulfonium salt having a polymerizable unsaturated bond, capable of generating a specific sulfonic acid and a similar iodonium salt. Patent Document 2 discloses a sulfonium salt having a sulfonic acid anion directly attached to the backbone.
Patent Documents 3 and 4 disclose resist materials comprising a polymer comprising amino-containing recurring units. Polymeric amines are highly effective for suppressing acid diffusion. Patent Document 5 discloses a resist material based on a polymer comprising recurring units of acid generator and recurring units of amine. It is a single component resist in which both an acid generator function and a quencher function are assigned to a common polymer. However, if the acid diffusion distance is too short, there arises the problem that both dissolution contrast and sensitivity drop.
CITATION LIST
  • Patent Document 1: JP-A 2006-045311 (U.S. Pat. No. 7,482,108)
  • Patent Document 2: JP-A 2006-178317
  • Patent Document 3: JP-A 2008-133312
  • Patent Document 4: JP-A 2009-181062
  • Patent Document 5: JP-A 2011-039266
  • Non-Patent Document 1: SPIE Vol. 6520 65203L-1 (2007)
SUMMARY OF INVENTION
An object of the present invention is to provide a positive resist composition which exhibits a higher sensitivity and resolution than conventional positive resist compositions, low edge roughness (LER, LWR) and small size variation, and forms a pattern of good profile after exposure and development, and a patterning process using the resist composition.
Making extensive investigations in search for a positive resist material capable of meeting the current requirements including high resolution, low edge roughness and small size variation, the inventors have found the following. To meet the requirements, the acid diffusion distance should be minimized. This invites a lowering of sensitivity and a drop of dissolution contrast, raising the problem that the resolution of a two-dimensional pattern such as hole pattern is reduced. Unexpectedly, when a polymer comprising recurring units of nitrogen-containing tertiary ester structure is used as a base polymer, the dissolution contrast is increased and at the same time, the acid diffusion distance is minimized. Better results are obtainable using the polymer as a base polymer in a chemically amplified positive resist composition.
Further, for improving the dissolution contrast, recurring units having a carboxyl or phenolic hydroxyl group in which the hydrogen is substituted by an acid labile group are incorporated into the base polymer. There is obtained a positive resist composition having a high sensitivity, a significantly increased contrast of alkali dissolution rate before and after exposure, a remarkable acid diffusion-suppressing effect, a high resolution, a good pattern profile after exposure, improved edge roughness, and small size variation. The composition is thus suitable as a fine pattern forming material for the manufacture of VLSIs and photomasks.
In one aspect, the invention provides a positive resist composition comprising a base polymer comprising recurring units having a carboxyl group in which the hydrogen is substituted by a nitrogen-containing tertiary hydrocarbon group.
Preferably, the nitrogen-containing tertiary hydrocarbon group is a nitrogen-containing tertiary cyclic hydrocarbon group.
Specifically, the recurring units have the formula (a).
Figure US11500289-20221115-C00001
Herein RA is hydrogen or methyl, X1 is each independently a single bond, phenylene, naphthylene, or a C1-C12 linking group containing an ester bond, ether bond or lactone ring, and R is a nitrogen-containing tertiary hydrocarbon group having the formula (a1) or (a2):
Figure US11500289-20221115-C00002
wherein R1 and R2 are each independently a C1-C6 alkyl group, C2-C6 alkenyl group or C2-C6 alkynyl group, R1 and R2 may bond together to form a ring with the carbon atom to which they are attached, R3 and R5 are each independently hydrogen, a C1—C straight, branched or cyclic alkyl group, C2-C10 straight or branched alkoxycarbonyl group, C3-C10 straight or branched alkenyloxycarbonyl group, or C8-C14 aralkyloxycarbonyl group, the group optionally containing an ether bond, R4 is a C1-C6 alkyl group. C2-C6 alkenyl group or C2-C6 alkynyl group, the circle Ra is a C2-C10 alicyclic group including the nitrogen atom, and the broken line designates a valence bond to the oxygen atom in formula (a).
In a preferred embodiment, the base polymer further comprises recurring units having a carboxyl group in which the hydrogen is substituted by an acid labile group and/or recurring units having a phenolic hydroxyl group in which the hydrogen is substituted by an acid labile group. More preferably, the recurring units having a carboxyl group in which the hydrogen is substituted by an acid labile group and the recurring units having a phenolic hydroxyl group in which the hydrogen is substituted by an acid labile group are recurring units having the formula (b1) and recurring units having the formula (b2), respectively.
Figure US11500289-20221115-C00003
Herein RA is each independently hydrogen or methyl, Y1 is a single bond, phenylene, naphthylene, or a C1-C12 linking group containing an ester bond, ether bond or lactone ring, Y2 is a single bond, ester bond or amide bond, R11 and R12 each are an acid labile group, R13 is fluorine, trifluoromethyl, cyano or C1-C6 alkyl, R14 is a single bond or a C1-C6 straight or branched alkanediyl group in which some carbon may be replaced by an ether bond or ester bond, a is 1 or 2, and b is an integer of 0 to 4.
The base polymer may further comprise recurring units containing an adhesive group selected from the group consisting of hydroxyl, carboxyl, lactone ring, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether bond, ester bond, sulfonic ester bond, cyano, amide, —O—C(═O)—S—, and —O—C(═O)—NH—.
The base polymer may further comprise recurring units of at least one type selected from recurring units having the formulae (d1) to (d3).
Figure US11500289-20221115-C00004
Herein RA is each independently hydrogen or methyl; Z1 is a single bond, phenylene, —O—Z11—, —C(═O)—O—Z11— or —C(═O)—NH—Z11—, Z11 is a C1-C6 alkanediyl group, C2-C6 alkenediyl group, or phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxyl moiety: Z2 is a single bond or a C1-C12 divalent group which may contain an ester bond, ether bond or lactone ring; Z3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—Z31—, —C(═O)—O—Z31— or —C(O)—NH—Z31—, Z31 is a C1-C6 alkanediyl group, C2-C6 alkenediyl group, or phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxyl moiety; Rf1 to Rf1 are each independently hydrogen, fluorine or trifluoromethyl, at least one of Rf1 to Rf1 being fluorine; R21 to R28 are each independently a C1-C20 monovalent hydrocarbon group which may contain a heteroatom, any two of R23, R24 and R25 or any two of R26, R27 and R28 may bond together to form a ring with the sulfur atom to which they are attached, and M− is a non-nucleophilic counter ion.
The positive resist composition may further comprise an acid generator, organic solvent, quencher, and/or surfactant.
In another aspect, the invention provides a pattern forming process comprising the steps of applying the positive resist composition defined above to form a resist film on a substrate, exposing the resist film to high-energy radiation, and developing the exposed resist film in a developer.
Typically, the high-energy radiation is i-line, KrF excimer laser. ArF excimer laser, EB, or EUV of wavelength 3 to 15 nm.
Advantageous Effects of Invention
The positive resist composition has a high decomposition efficiency of the acid generator, a remarkable acid diffusion-suppressing effect, a high sensitivity, and a high resolution, and forms a pattern of good profile with improved edge roughness and size variation after exposure and development. By virtue of these properties, the resist composition is fully useful in commercial application and best suited as a micropatterning material for photomasks by EB lithography or for VLSIs by EB or EUV lithography. The resist composition may be used not only in the lithography for forming semiconductor circuits, but also in the formation of mask circuit patterns, micromachines, and thin-film magnetic head circuits.
DESCRIPTION OF EMBODIMENTS
As used herein, the singular forms “a” “an” and “the” include plural referents unless the context clearly dictates otherwise. “Optional” or “optionally” means that the subsequently described event or circumstances may or may not occur, and that description includes instances where the event or circumstance occurs and instances where it does not. The notation (Cn-Cm) means a group containing from n to m carbon atoms per group. Me stands for methyl, and Ac for acetyl.
The abbreviations and acronyms have the following meaning.
    • EB: electron beam
    • EUV: extreme ultraviolet
    • Mw: weight average molecular weight
    • Mn: number average molecular weight
    • Mw/Mn: molecular weight distribution or dispersity
    • GPC: gel permeation chromatography
    • PEB: post-exposure bake
    • PAG: photoacid generator
    • LWR: line width roughness
    • LER: line edge roughness
    • CDU: critical dimension uniformity
Positive Resist Composition
One embodiment of the invention is a positive resist composition comprising a base polymer comprising recurring units having a carboxyl group in which the hydrogen is substituted by a nitrogen-containing tertiary hydrocarbon group. The nitrogen-containing tertiary hydrocarbon group is preferably a nitrogen-containing tertiary cyclic hydrocarbon group because a resist film having a satisfactory acid diffusion-suppressing effect and a high dissolution contrast is obtainable.
Preferably, the recurring units have the formula (a). The recurring units having formula (a) are also referred to as recurring units (a).
Figure US11500289-20221115-C00005
In formula (a), RA is hydrogen or methyl. X1 is each independently a single bond, phenylene, naphthylene, or a C1-C12 linking group containing an ester bond, ether bond or lactone ring.
Examples of the monomer from which recurring units (a) are derived are shown below, but not limited thereto. Herein RA is as defined above, and R will be defined below.
Figure US11500289-20221115-C00006
Figure US11500289-20221115-C00007
Figure US11500289-20221115-C00008
In formula (a), R is a nitrogen-containing tertiary hydrocarbon group having the formula (a1) or (a2).
Figure US11500289-20221115-C00009
In formulae (a1) and (a2), R1 and R2 are each independently a C1-C6 alkyl group, C2—C alkenyl group or C2-C6 alkynyl group. R and R2 may bond together to form a ring with the carbon atom to which they are attached. R3 and R5 are each independently hydrogen, a C1-C9 straight or branched alkyl group, C2-C10 straight or branched alkoxycarbonyl group, C3-C10 straight or branched alkenyloxycarbonyl group, or C8-C14 aralkyloxycarbonyl group, the group optionally containing an ether bond. R4 is a C1-C6 alkyl group, C2-C6 alkenyl group or C2-C6 alkynyl group. The circle Ra is an alicyclic group of 2 to 10 carbon atoms including the nitrogen atom. The broken line designates a valence bond to the oxygen atom in formula (a).
Of the groups represented by R1 and R2, the C1-C6 alkyl group may be straight, branched or cyclic and examples thereof include methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, and cyclohexyl. The C2-C6 alkenyl group may be straight, branched or cyclic and examples thereof include vinyl, 1-propenyl, 2-propenyl, butenyl, hexenyl, and cyclohexenyl. The C2-C6 alkynyl group may be straight, branched or cyclic and examples thereof include ethynyl and butynyl. Inter alia, R1 and R2 are preferably methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, vinyl or ethynyl.
Of the groups represented by R3 and R5, examples of the straight or branched C1-C9 alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, and n-nonyl. Examples of the straight or branched C2-C10 alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, tert-pentyloxycarbonyl, neopentyloxycarbonyl, and n-hexyloxycarbonyl. Examples of the straight or branched C3-C10 alkenyloxycarbonyl groups include vinyloxycarbonyl and 2-propenyloxycarbonyl. Examples of the C8-C14 alkenyloxycarbonyl groups include benzyloxycarbonyl and phenethyloxycarbonyl. Inter alia, R3 and R5 are preferably hydrogen, methyl, ethyl, isopropyl, tert-butyloxycarbonyl, tert-pentyloxycarbonyl, 2-propenyloxycarbonyl or benzyloxycarbonyl.
Examples of the C1-C6 alkyl. C2-C6 alkenyl and C2-C6 alkynyl groups represented by R4 are as exemplified above for R1 and R2. R4 is preferably methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, vinyl or ethynyl.
Of the monomers from which recurring units (a) are derived, the monomers having a group of formula (a1) are exemplified below, but not limited thereto. Herein, RA and X1 are as defined above.
Figure US11500289-20221115-C00010
Figure US11500289-20221115-C00011
Of the monomers from which recurring units (a) are derived, the monomers having a group of formula (a2) are exemplified below, but not limited thereto. Herein, RA and X1 are as defined above.
Figure US11500289-20221115-C00012
Figure US11500289-20221115-C00013
Figure US11500289-20221115-C00014
The recurring unit (a) functions as a quencher due to the inclusion of nitrogen atom. In this sense, the base polymer may be referred to as a quencher-bound polymer. The quencher-bound polymer has the advantages of a remarkable acid diffusion-suppressing effect and improved resolution. In addition, the recurring unit (a) is an acid labile group unit due to the inclusion of a tertiary ester structure. Although an ordinary acid labile group unit follows an acid-aided polarity switch mechanism, the recurring unit (a) has not only the polarity switch function, but also the acid diffusion suppressing function. This enables to enhance dissolution contrast while suppressing acid diffusion.
For further enhancing dissolution contrast, the base polymer may further comprise recurring units having a carboxyl group in which the hydrogen is substituted by an acid labile group, referred to as recurring units (b1), hereinafter, and/or recurring units having a phenolic hydroxyl group in which the hydrogen is substituted by an acid labile group, referred to as recurring units (b2), hereinafter.
The preferred recurring units (b1) and (b2) are recurring units having the formulae (b1) and (b2), respectively.
Figure US11500289-20221115-C00015
In formulae (b1) and (b2), RA is each independently hydrogen or methyl. Y1 is a single bond, phenylene, naphthylene, or a C1-C12 linking group containing an ester bond, ether bond or lactone ring. Y2 is a single bond, ester bond or amide bond. R11 and R12 each are an acid labile group. R13 is fluorine, trifluoromethyl, cyano or a C1-C6 alkyl group. R14 is a single bond or a C1-C6 straight or branched alkanediyl group in which some carbon may be replaced by an ether bond or ester bond. The subscript a is 1 or 2, and b is an integer of 0 to 4.
Examples of the monomer from which recurring units (b1) are derived are shown below, but not limited thereto. Herein RA and R11 are as defined above.
Figure US11500289-20221115-C00016
Figure US11500289-20221115-C00017
Figure US11500289-20221115-C00018
Examples of the monomer from which recurring units (b2) are derived are shown below, but not limited thereto. Herein RA and R12 are as defined above.
Figure US11500289-20221115-C00019
The acid labile groups represented by R11 and R12 may be selected from a variety of such groups, for example, groups of the following formulae (AL-1) to (AL-3).
Figure US11500289-20221115-C00020
In formula (AL-1), RL10 is a C4-C20, preferably C4-C5 tertiary hydrocarbon group, a trialkylsilyl group in which each alkyl moiety has 1 to 6 carbon atoms, a C4-C20 alkyl group containing a carbonyl moiety or ester bond, or a group of formula (AL-3). Al is an integer of 0 to 6.
The tertiary hydrocarbon group may be branched or cyclic, and examples thereof include tert-butyl, tert-pentyl, 1,1-diethylpropyl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, l-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl, 2-tetrahydropyranyl, and 2-tetrahydrofuranyl. Examples of the trialkylsilyl group include trimethylsilyl, triethylsilyl, and dimethyl-tert-butylsilyl. The alkyl group containing a carbonyl moiety or ester bond may be straight, branched or cyclic, preferably cyclic and examples thereof include 3-oxocyclohexyl, 4-methyl-2-oxooxan-4-yl, and 5-methyl-2-oxooxolan-5-yl.
Examples of the acid labile group having formula (AL-1) include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-pentyloxycarbonyl, tert-pentyloxycarbonylmethyl, 1,1-diethylpropyloxycarbonyl, 1,1-diethylpropyloxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentenyloxycabonylmtethyl, 1-ethoxyethoxycarbonyhnlmethyl, 2-tetrahydropyranyloxycarbonyhulmethyl, and 2-tetrahydrofuranyloxycarbonylmethyl.
Other examples of the acid labile group having formula (AL-1) include groups having the formulae (AL-1)-1 to (AL-1)-10.
Figure US11500289-20221115-C00021
Herein A1 is as defined above. RL8 is each independently a C1-C10 alkyl group or C6-C20 aryl group. RL9 is hydrogen or a C1-C10 alkyl group. RL10 is a C2-C10 alkyl group or C6-C20 aryl group. The alkyl group may be straight, branched or cyclic.
In formula (AL-2), RU and RL2 are each independently hydrogen or a C1-C18, preferably C1-C10 alkyl group. The alkyl group may be straight, branched or cyclic and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl and n-octyl. RL4 is a C1-C18, preferably C1-C10 monovalent hydrocarbon group which may contain a heteroatom such as oxygen. The monovalent hydrocarbon group may be straight, branched or cyclic and typical examples thereof include C1-C18 alkyl groups, in which some hydrogen may be substituted by hydroxyl, alkoxy, oxo, amino or alkylamino. Examples of the substituted alkyl group are shown below.
Figure US11500289-20221115-C00022
A pair of RL2 and RL3, RL2 and RL4, or RL3 and RL4 may bond together to form a ring with the carbon atom or carbon and oxygen atoms to which they are attached. A ring-forming combination of RL2 and RL3, RL2 and RL4, or RL3 and RL4 is each independently a C1-C18, preferably C1-C10 straight or branched alkanediyl group. The ring thus formed is preferably of 3 to 10, more preferably 4 to 10 carbon atoms.
Of the acid labile groups having formula (AL-2), suitable straight or branched groups include those having formulae (AL-2)-1 to (AL-2)-69, but are not limited thereto.
Figure US11500289-20221115-C00023
Figure US11500289-20221115-C00024
Figure US11500289-20221115-C00025
Figure US11500289-20221115-C00026
Figure US11500289-20221115-C00027
Figure US11500289-20221115-C00028
Of the acid labile groups having formula (AL-2), suitable cyclic groups include tetrahydrofuran-2-yl 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl, and 2-methyltetrahydropyran-2-yl.
Also included are acid labile groups having the following formulae (AL-2a) and (AL-2b). The base polymer may be crosslinked within the molecule or between molecules with these acid labile groups.
Figure US11500289-20221115-C00029
In formulae (AL-2a) and (AL-2b), RL11 and RL12 are each independently hydrogen or a C1-C8 alkyl group which may be straight, branched or cyclic. Also, RL11 and RL12 may bond together to form a ring with the carbon atom to which they are attached, and in this case, RL11 and RL12 are each independently a C1-C8 straight or branched alkanediyl group. RL13 is each independently a C1-C10 alkanediyl group which may be straight, branched or cyclic. B1 and D1 are each independently an integer of 0 to 10, preferably 0 to 5, and C1 is an integer of 1 to 7, preferably 1 to 3.
In formulae (AL-2a) and (AL-2b), LA is a (C1+1)-valent C1-C50 aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group. In these groups, some carbon may be replaced by a heteroatom-containing moiety, or some carbon-bonded hydrogen may be substituted by a hydroxyl, carboxyl, acyl moiety or fluorine. LA is preferably a C1-C20 alkanediyl, alkanetriyl, alkanetetrayl, or C6-C30 arylene group. The alkanediyl, alkanetriyl, and alkanetetrayl groups may be straight, branched or cyclic. LB is —CO—O—, —NHCO—O— or —NHCONH—.
Examples of the crosslinking acetal groups having formulae (AL-2a) and (AL-2b) include groups having the formulae (AL-2)-70 to (AL-2)-77.
Figure US11500289-20221115-C00030
In formula (AL-3), RL5, RL6 and RL7 are each independently a C1-C20 monovalent hydrocarbon group which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. The monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof include C1-C20 alkyl groups and C2-C20 alkenyl groups. A pair of RL5 and RL6, RL5 and RL7, or RL6 and RL7 may bond together to form a C3-C20 aliphatic ring with the carbon atom to which they are attached.
Examples of the group having formula (AL-3) include tert-butyl, 1,1-diethylpropyl, 1-ethylnorbornyl, 1-methylcyclopentyl, 1-isopropylcyclopentyl, 1-ethycyclopentyl, l-methylcyclohexyl 2-(2-methyl)adamantyl, 2-(2-ethyl)adamantyl, and tert-pentyl.
Examples of the group having formula (AL-3) also include groups having the formulae (AL-3)-1 to (AL-3)-18.
Figure US11500289-20221115-C00031
Figure US11500289-20221115-C00032
Figure US11500289-20221115-C00033
In formulae (AL-3)-1 to (AL-3)-18, RL14 is each independently a C1-C8 alkyl group or C6-C20 aryl group. RL15 and RL17 are each independently hydrogen or a C1-C20 alkyl group. RL16 is a C6-C20 aryl group. The alkyl group may be straight, branched or cyclic. Typical of the aryl group is phenyl.
Other examples of the group having formula (AL-3) include groups having the formulae (AL-3)-19 and (AL-3)-20. The base polymer may be crosslinked within the molecule or between molecules with these acid labile groups.
Figure US11500289-20221115-C00034
In formulae (AL-3)-19 and (AL-3)-20, RL14 is as defined above. RL18 is a (E1+1)-valent C1-C20 alkanediyl group or (E1+1)-valent C6-C20 arylene group, which may contain a heteroatom such as oxygen, sulfur or nitrogen. The alkanediyl group may be straight, branched or cyclic. E1 is an integer of 1 to 3.
Examples of the monomer from which recurring units containing an acid labile group of formula (AL-3) are derived include (meth)acrylates having an exo-form structure represented by the formula (AL-3)-21.
Figure US11500289-20221115-C00035
In formula (AL-3)-21, RA is as defined above. RLc1 is a C1-C5 alkyl group or an optionally substituted C6-C20 aryl group; the alkyl group may be straight, branched or cyclic. RLc2 to RLc11 are each independently hydrogen or a C1-C15 monovalent hydrocarbon group which may contain a heteroatom; oxygen is a typical heteroatom. Suitable monovalent hydrocarbon groups include C1-C15 alkyl groups and C6-C15 aryl groups. Alternatively, a pair of RLc2 and RLc3, RLc4 and RLc6, RLc4 and RLc7, RLc5 and RLc7, RLc5 and RLc11, RLc6 and RLc10, RLc8 and RLc9, or RLc9 and RLc10, taken together, may form a ring with the carbon atom to which they are attached, and in this event, the ring-forming combination is a C1-C15 divalent hydrocarbon group which may contain a heteroatom. Also, a pair of RLc2 and RLc11, RLc8 and RLc11, or RLc4 and RLc6 which are attached to vicinal carbon atoms may bond together directly to form a double bond. The formula also represents an enantiomer.
Examples of the monomer from which recurring units having formula (AL-3)-21 are derived are described in U.S. Pat. No. 6,448,420 (JP-A 2000-327633). Illustrative non-limiting examples of suitable monomers are given below. RA is as defined above.
Figure US11500289-20221115-C00036
Figure US11500289-20221115-C00037
Also included in the recurring units having an acid labile group of formula (AL-3) are recurring units of (meth)acrylate having a furandiyl, tetrahydrofurandiyl or oxanorbornauediyl group as represented by the following formula (AL-3)-22.
Figure US11500289-20221115-C00038
In formula (AL-3)-22, RA is as defined above. RLc12 and RLc13 are each independently a C1-C10 monovalent hydrocarbon group, or RLc12 and RLc13, taken together, may form an aliphatic ring with the carbon atom to which they are attached. RLc14 is furandiyl, tetrahydrofurandiyl or oxanorbornanediyl. RLc15 is hydrogen or a C1-C10 monovalent hydrocarbon group which may contain a heteroatom. The monovalent hydrocarbon group may be straight, branched or cyclic, and examples thereof include C1-C10 alkyl groups.
Examples of the monomer from which the recurring units having formula (AL-3)-22 are derived are shown below, but not limited thereto. Herein RA is as defined above.
Figure US11500289-20221115-C00039
Figure US11500289-20221115-C00040
Figure US11500289-20221115-C00041
Figure US11500289-20221115-C00042
In the base polymer, recurring units (c) having an adhesive group may be incorporated. The adhesive group is selected from hydroxyl, carboxyl, lactone ring, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether, ester, sulfonic acid ester, cyano, amide, —O—C(═O)—S— and —O—C(═O)—NH—.
Examples of the monomer from which recurring units (c) are derived are given below, but not limited thereto. Herein RA is as defined above.
Figure US11500289-20221115-C00043
Figure US11500289-20221115-C00044
Figure US11500289-20221115-C00045
Figure US11500289-20221115-C00046
Figure US11500289-20221115-C00047
Figure US11500289-20221115-C00048
Figure US11500289-20221115-C00049
Figure US11500289-20221115-C00050
Figure US11500289-20221115-C00051
Figure US11500289-20221115-C00052
Figure US11500289-20221115-C00053
Figure US11500289-20221115-C00054
Figure US11500289-20221115-C00055
Figure US11500289-20221115-C00056
Figure US11500289-20221115-C00057
Figure US11500289-20221115-C00058
Figure US11500289-20221115-C00059
Figure US11500289-20221115-C00060
Figure US11500289-20221115-C00061
Figure US11500289-20221115-C00062
In a further embodiment, recurring units (d) derived from an onium salt having a polymerizable unsaturated bond may be incorporated in the base polymer. The preferred recurring units (d) are recurring units having the following formulae (d1), (d2) and (d3). These units are simply referred to as recurring units (d1), (d2) and (d3), which may be used alone or in combination of two or more types.
Figure US11500289-20221115-C00063
In formulae (d1) to (d3), RA is each independently hydrogen or methyl. Z1 is a single bond, phenylene. —O—Z11—, —C(═O)—O—Z11— or —C(═O)—NH—Z11—, wherein Z11 is a C1-C6 alkanediyl group, C2-C6 alkenediyl group, or phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxyl moiety. Z2 is a single bond or a C1-C12 divalent group which may contain an ester bond, ether bond or lactone ring. Z3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—Z31—, —C(═O)—O—Z31— or —C(═O)—NH—Z31—, wherein Z31 is a C1-C6 alkanediyl group, C2—C alkenediyl group, or phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxyl moiety.
In formula (d2), Rf1 to Rf4 are each independently hydrogen, fluorine or trifluoromethyl, at least one of Rf1 to Rf4 being fluorine. Preferably at least one of Rf3 and Rf4 is fluorine, most preferably both Rf3 and Rf4 are fluorine.
In formulae (d1) to (d3), R21 to R22 are each independently a C1-C20 monovalent hydrocarbon group which may contain a heteroatom, any two of R23, R24 and R25 or any two of R26, R27 and R28 may bond together to form a ring with the sulfur atom to which they are attached. The monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof include C1-C12 alkyl, C6-C12 aryl, and C7-C20 aralkyl groups. In these groups, some or all hydrogen may be substituted by C1-C10 alkyl, halogen, trifluoromethyl, cyano, nitro, hydroxyl mercapto, C1-C10 alkoxy, C2-C10 alkoxycarbonyl, or C2-C10 acyloxy moiety, or some carbon may be replaced by a carbonyl moiety, ether bond or ester bond.
In formula (d1), M− is a non-nucleophilic counter ion. Examples of the non-nucleophilic counter ion include halide ions such as chloride and bromide ions; fluoroalkylsulfonate ions such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; arylsulfonate ions such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkylsulfonate ions such as mesylate and butanesulfonate: imide ions such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide and bis(perfluorobutylsulfonyl)imide; methide ions such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide.
Also included are sulfonate ions having fluorine substituted at α-position as represented by the formula (K-1) and sulfonate ions having fluorine substituted at α-position and trifluoromethyl at β-position as represented by the formula (K-2).
Figure US11500289-20221115-C00064
In formula (K-1), R31 is hydrogen, or a C1-C20 alkyl group, C2-C20 alkenyl group, or C6-C20 aryl group, which may contain an ether bond, ester bond, carbonyl moiety, lactone ring, or fluorine atom. The alkyl and alkenyl groups may be straight, branched or cyclic.
In formula (K-2), R32 is hydrogen, or a C1-C30 alkyl group, C2-C30 acyl group, C2-C20 alkenyl group, C6-C20 aryl group or C6-C20 aryloxy group, which may contain an ether bond, ester bond, carbonyl moiety or lactone ring. The alkyl, acyl and alkenyl groups may be straight, branched or cyclic.
Examples of the monomer from which recurring unit (d1) is derived are shown below, but not limited thereto. RA and M− are as defined above.
Figure US11500289-20221115-C00065
Figure US11500289-20221115-C00066
Figure US11500289-20221115-C00067
Figure US11500289-20221115-C00068
Examples of the monomer from which recurring unit (d2) is derived are shown below, but not limited thereto. RA is as defined above.
Figure US11500289-20221115-C00069
Figure US11500289-20221115-C00070
Figure US11500289-20221115-C00071
Figure US11500289-20221115-C00072
Figure US11500289-20221115-C00073
Figure US11500289-20221115-C00074
Figure US11500289-20221115-C00075
Figure US11500289-20221115-C00076
Examples of the monomer from which recurring unit (d3) is derived are shown below, but not limited thereto. RA is as defined above.
Figure US11500289-20221115-C00077
Figure US11500289-20221115-C00078
Figure US11500289-20221115-C00079
Figure US11500289-20221115-C00080
Figure US11500289-20221115-C00081
Recurring units (d1) to (d3) have the function of acid generator. The attachment of an acid generator to the polymer main chain is effective in restraining acid diffusion, thereby preventing a reduction of resolution due to blur by acid diffusion. Also LWR is improved since the acid generator is uniformly distributed. When a base polymer comprising recurring units (d) is used, an acid generator of addition type (to be described later) may be omitted.
Besides the recurring units described above, further recurring units (e) may be incorporated in the base polymer, examples of which include styrene, acenaphthylene, indene, coumarin, and coumarone.
In the base polymer comprising recurring units (a1), (a2), (b1), (b2), (c), (d1), (d2), (d3), and (e), a fraction of these units is: preferably 0<a<1.0, 0≤b1≤0.9, 0≤b2≤0.9, 0≤b1+b2≤0.9, 0≤c≤0.9, 0≤d1≤0.5, 0≤d2≤0.5, 0≤d3≤0.5, 0≤d1+d2+d3≤0.5, and 0≤e≤0.5;
more preferably 0.01≤a≤0.8, 0≤b1≤0.8, 0≤b2≤0.8, 0≤b1+b2≤0.8, 0≤c≤0.8, 0≤d1≤0.4, 0≤d2≤0.4, 0≤d3≤0.4, 0≤d1+d2+d3≤0.4, and 0≤e≤0.4; and even more preferably 0≤a1≤0.7, 0≤a2≤0.7, 0.02≤a1+a2≤0.7, 0≤b1≤0.7, 0≤b2≤0.7, 0≤b1+b2≤0.7, 0≤c≤0.7, 0≤d1≤0.3, 0≤d2≤0.3, 0≤d3≤0.3, 0≤d1+d2+d3≤0.3, and 0≤e≤0.3. Notably, a1+a2+b1+b2+c+d1+d2+d3+e=1.0.
The base polymer may be synthesized by any desired methods, for example, by dissolving one or more monomers selected from the monomers corresponding to the foregoing recurring units in an organic solvent, adding a radical polymerization initiator thereto, and heating for polymerization. Examples of the organic solvent which can be used for polymerization include toluene, benzene, tetrahydrofuran (THF), diethyl ether, and dioxane. Examples of the polymerization initiator used herein include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. Preferably the reaction temperature is 50 to 80° C., and the reaction time is 2 to 100 hours, more preferably 5 to 20 hours.
In the case of a monomer having a hydroxyl group, the hydroxyl group may be replaced by an acetal group susceptible to deprotection with acid, typically ethoxyethoxy, prior to polymerization, and the polymerization be followed by deprotection with weak acid and water. Alternatively, the hydroxyl group may be replaced by an acetyl, formyl, pivaloyl or similar group prior to polymerization, and the polymerization be followed by alkaline hydrolysis.
When hydroxystyrene or hydroxyvinylnaphthalene is copolymerized, an alternative method is possible. Specifically, acetoxystyrene or acetoxyvinylnaphthalene is used instead of hydroxystyrene or hydroxyvinylnaphthalene, and after polymerization, the acetoxy group is deprotected by alkaline hydrolysis, for thereby converting the polymer product to hydroxystyrene or hydroxyvinylnaphthalene. For alkaline hydrolysis, a base such as aqueous ammonia or triethylamine may be used. Preferably the reaction temperature is −20° C. to 100° C., more preferably 0° C. to 60° C., and the reaction time is 0.2 to 100 hours, more preferably 0.5 to 20 hours.
The base polymer should preferably have a weight average molecular weight (Mw) in the range of 1,000 to 500,000, and more preferably 2,000 to 30,000, as measured by GPC versus polystyrene standards using tetrahydrofuran (THF) solvent. With too low a Mw, the resist composition may become less heat resistant. A polymer with too high a Mw may lose alkaline solubility and give rise to a footing phenomenon after pattern formation.
If a base polymer has a wide molecular weight distribution or dispersity (Mw/Mn), which indicates the presence of lower and higher molecular weight polymer fractions, there is a possibility that foreign matter is left on the pattern or the pattern profile is degraded. The influences of Mw and Mw/Mn become stronger as the pattern rule becomes finer. Therefore, the base polymer should preferably have a narrow dispersity (Mw/Mn) of 1.0 to 2.0, especially 1.0 to 1.5, in order to provide a resist composition suitable for micropatterning to a small feature size.
The base polymer may be a blend of two or more polymers which differ in compositional ratio, Mw or Mw/Mn. It may also be a blend of a polymer comprising recurring units (a) and a polymer comprising recurring units (b1) and/or (b2), but not recurring units (a).
Acid Generator
The positive resist composition may contain an acid generator capable of generating a strong acid, also referred to as acid generator of addition type. As used herein, the “strong acid” is a compound having a sufficient acidity to induce deprotection reaction of acid labile groups on the base polymer. The acid generator is typically a compound (PAG) capable of generating an acid upon exposure to actinic ray or radiation. Although the PAG used herein may be any compound capable of generating an acid upon exposure to high-energy radiation, those compounds capable of generating sulfonic acid, imidic acid (imide acid) or methide acid are preferred. Suitable PAGs include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate acid generators. Suitable PAGs are as exemplified in U.S. Pat. No. 7,537,880 (JP-A 2008-111103, paragraphs [0122]-[0142]).
Also sulfonium salts having the formula (1-1) and iodonium salts having the formula (1-2) are useful PAGs.
Figure US11500289-20221115-C00082
In formulae (1-1) and (1-2), R101 to R105 are each independently a C1-C2 monovalent hydrocarbon group which may contain a heteroatom. Any two of R101, R102 and R103 may bond together to form a ring with the sulfur atom to which they are attached. The monovalent hydrocarbon group may be straight, branched or cyclic, and examples thereof are as exemplified above for R21 to R28 in formulae (d1) to (d3).
Examples of the cation of the sulfonium salt having formula (1-1) are shown below, but not limited thereto.
Figure US11500289-20221115-C00083
Figure US11500289-20221115-C00084
Figure US11500289-20221115-C00085
Figure US11500289-20221115-C00086
Figure US11500289-20221115-C00087
Figure US11500289-20221115-C00088
Figure US11500289-20221115-C00089
Figure US11500289-20221115-C00090
Figure US11500289-20221115-C00091
Figure US11500289-20221115-C00092
Figure US11500289-20221115-C00093
Figure US11500289-20221115-C00094
Figure US11500289-20221115-C00095
Figure US11500289-20221115-C00096
Figure US11500289-20221115-C00097
Figure US11500289-20221115-C00098
Figure US11500289-20221115-C00099
Figure US11500289-20221115-C00100
Figure US11500289-20221115-C00101
Figure US11500289-20221115-C00102
Figure US11500289-20221115-C00103
Figure US11500289-20221115-C00104
Figure US11500289-20221115-C00105
Figure US11500289-20221115-C00106
Figure US11500289-20221115-C00107
Figure US11500289-20221115-C00108
Figure US11500289-20221115-C00109
Figure US11500289-20221115-C00110
Figure US11500289-20221115-C00111
Figure US11500289-20221115-C00112
Figure US11500289-20221115-C00113
Examples of the cation of the iodonium salt having formula (1-2) are shown below, but not limited thereto.
Figure US11500289-20221115-C00114
Figure US11500289-20221115-C00115
Figure US11500289-20221115-C00116
In formulae (1-1) and (1-2). X is an anion selected from the formulae (1A) to (1D).
Figure US11500289-20221115-C00117
In formula (1A), Rfa is fluorine or a C1-C40 monovalent hydrocarbon group which may contain a heteroatom. The monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof are as will be exemplified below for R107.
Of the anions of formula (1A), a structure having formula (1A′) is preferred.
Figure US11500289-20221115-C00118
In formula (1A′), R106 is hydrogen or trifluoromethyl, preferably trifluoromethyl. R107 is a C1-C3 monovalent hydrocarbon group which may contain a heteroatom. Suitable heteroatoms include oxygen, nitrogen, sulfur and halogen, with oxygen being preferred. Of the monovalent hydrocarbon groups, those of 6 to 30 carbon atoms are preferred because a high resolution is available in fine pattern formation.
The monovalent hydrocarbon group may be straight, branched or cyclic. Examples thereof include straight or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, icosanyl; monovalent saturated alicyclic hydrocarbon groups such as 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecanyl, tetracyclododecanylmethyl, dicyclohexylmethyl; monovalent unsaturated aliphatic hydrocarbon groups such as allyl and 3-cyclohexenyl; aryl groups such as phenyl, l-naphthyl and 2-naphthyl; aralkyl groups such as benzyl and diphenyhlmethyl. Exemplary heteroatom-containing monovalent hydrocarbon groups are tetrahydrofuryl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl. Also included are the foregoing groups in which some hydrogen is substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or in which some carbon is replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxyl, cyano, carbonyl, ether bond, ester bond, sulfonic acid ester bond, carbonate, lactone ring, sultone ring, carboxylic acid anhydride or haloalkyl moiety.
With respect to the synthesis of the sulfonium salt having an anion of formula (1A′), reference is made to JP-A 2007-145797, JP-A 2008-106045, JP-A 2009-007327, and JP-A 2009-258695. Also useful are the sulfonium salts described in JP-A 2010-215608, JP-A 2012-041320, JP-A 2012-106986, and JP-A 2012-153644.
Examples of the anion having formula (1A) are shown below, but not limited thereto.
Figure US11500289-20221115-C00119
Figure US11500289-20221115-C00120
Figure US11500289-20221115-C00121
Figure US11500289-20221115-C00122
In formula (1B), Rfb1 and Rfb2 are each independently fluorine or a C1-C40 monovalent hydrocarbon group which may contain a heteroatom. The monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof are as exemplified above for R107. Preferably Rfb1 and Rfb2 each are fluorine or a straight C1-C4 fluorinated alkyl group. A pair of Rfb1 and Rfb2 may bond together to form a ring with the linkage (—CF2—SO2—N−—SO2—CF2—) to which they are attached, and preferably the pair is a fluorinated ethylene or fluorinated propylene group.
In formula (1C), Rfc1. Rfc2 and Rfc3 are each independently fluorine or a C1-C40 monovalent hydrocarbon group which may contain a heteroatom. The monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof are as exemplified above for R107. Preferably Rfc1, Rfc2 and Rfc3 each are fluorine or a straight C1-C4 fluorinated alkyl group. A pair of Rfc1 and Rfc2 may bond together to form a ring with the linkage (—CF2—SO2—C−—SO2—CF2—) to which they are attached, and preferably the pair is a fluorinated ethylene or fluorinated propylene group.
In formula (1D), Rfd is a C1-C40 monovalent hydrocarbon group which may contain a heteroatom. The monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof are as exemplified above for R107.
With respect to the synthesis of the sulfonium salt having an anion of formula (1D), reference is made to JP-A 2010-215608 and JP-A 2014-133723.
Examples of the anion having formula (1D) are shown below, but not limited thereto.
Figure US11500289-20221115-C00123
Figure US11500289-20221115-C00124
The compound having the anion of formula (1D) has a sufficient acid strength to cleave acid labile groups in the base polymer because it is free of fluorine at α-position of sulfo group, but has two trifluoromethyl groups at 3-position. Thus the compound is a useful PAG.
A compound having the formula (2) is also a useful PAG.
Figure US11500289-20221115-C00125
In formula (2), R201 and R202 are each independently a C1-C30 monovalent hydrocarbon group which may contain a heteroatom. R203 is a C1-C30 divalent hydrocarbon group which may contain a heteroatom. Any two of R201, R202 and R203 may bond together to form a ring with the sulfur atom to which they are attached. L is a single bond, ether bond or a C1-C20 divalent hydrocarbon group which may contain a heteroatom. XA, XB, XC and XD are each independently hydrogen, fluorine or trifluoromethyl, with the proviso that at least one of XA, XB, XC and XD is fluorine or trifluoromethyl, and k is an integer of 0 to 3.
The monovalent hydrocarbon group may be straight, branched or cyclic. Examples thereof include straight or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, 2-ethylhexyl; monovalent saturated cyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbormyl, oxanorbornyl, tricyclo[5.2.1.02,6]decanyl, adamantyl; aryl groups such as phenyl, naphthyl and anthracenyl. Also included are the foregoing groups in which some hydrogen is substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or in which some carbon is replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxyl, cyano, carbonyl, ether bond, ester bond, sulfonic acid ester bond, carbonate bond, lactone ring, sultone ring, carboxylic acid anhydride or haloalkyl moiety.
The divalent hydrocarbon group may be straight, branched or cyclic. Examples thereof include straight or branched alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl; divalent saturated cyclic hydrocarbon groups such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl; and divalent unsaturated cyclic hydrocarbon groups such as phenylene and naphthylene. Also included are the foregoing groups in which some hydrogen is substituted by an alkyl group such as methyl, ethyl, propyl, n-butyl or tert-butyl, or in which some hydrogen is substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or in which some carbon is replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxyl, cyano, carbonyl, ether bond, ester bond, sulfonic acid ester bond, carbonate, lactone ring, sultone ring, carboxylic acid anhydride or haloalkyl moiety. The preferred heteroatom is oxygen.
Of the PAGs having formula (2), those having formula (2′) are preferred.
Figure US11500289-20221115-C00126
In formula (2′), L is as defined above. “A” is hydrogen or trifluoromethyl, preferably trifluoromethyl. R301, R302 and R303 are each independently hydrogen or a C1-C20 monovalent hydrocarbon group which may contain a heteroatom. The monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof are as exemplified above for R107. The subscripts x and y each are an integer of 0 to 5, and z is an integer of 0 to 4.
Examples of the PAG having formula (2) are shown below, but not limited thereto. Herein “A” is as defined above.
Figure US11500289-20221115-C00127
Figure US11500289-20221115-C00128
Figure US11500289-20221115-C00129
Figure US11500289-20221115-C00130
Figure US11500289-20221115-C00131
Figure US11500289-20221115-C00132
Of the foregoing PAGs, those compounds having an anion of formula (1A′) or (1D) are especially preferred because of reduced acid diffusion and high solubility in resist solvent, and those compounds having an anion of formula (2′) are especially preferred because of minimized acid diffusion.
Also sulfonium and iodonium salts having an anion containing an iodized or brominated aromatic ring are useful PAGs. These salts typically have the formulae (3-1) and (3-2).
Figure US11500289-20221115-C00133
In formulae (3-1) and (3-2), X is iodine or bromine. When s is at least 2, groups X may be identical or different.
L1 is a single bond, ether bond, ester bond, or a C1-C6 alkanediyl group which may contain an ether bond or ester bond. The alkanediyl group may be straight, branched or cyclic.
R401 is hydroxyl, carboxyl, fluorine, chlorine, bromine, amino or a C1-C20 alkyl group, C1-C20 alkoxy group, C2-C10 alkoxycarbonyl, C2-C20 acyloxy group, or C1-C20 alkylsulfonyloxy group, which may contain fluorine, chlorine, bromine, hydroxyl, amino or C1-C10 alkoxy moiety, or —NR401A—C(═O)—R401B or —NR401A—C(═O)—O—R401B. R401A is hydrogen or a C1-C6 alkyl group which may contain halogen, hydroxyl, C1-C6 alkoxy, C2-C6 acyl or C2-C6 acyloxy moiety, R401B is a C1-C16 alkyl group, C2-C16 alkenyl group or C6-C12 aryl group, which may contain halogen, hydroxyl, a C1-C6 alkoxy, C2-C6 acyl or C2-C6 acyloxy moiety. The alkyl, alkoxy, alkoxycarbonyl, acyloxy, acyl and alkenyl groups may be straight, branched or cyclic. When t is at least 2, groups R401 may be identical or different.
Inter alia, R401 is preferably selected from hydroxyl —NR401A—C(═O)—R401B, —NR401A—C(═O)—R401B, fluorine, chlorine, bromine, methyl, and methoxy.
R402 is a single bond or a C1-C20 divalent linking group in case of r=1, and a C1-C20 tri- or tetravalent linking group in case of r=2 or 3. The linking group may contain oxygen, sulfur or nitrogen.
Rf11 to Rf14 are each independently hydrogen, fluorine or trifluaromethyl, at least one thereof being fluorine or trifluoromethyl. Also Rf11 and Rf12, taken together, may form a carbonyl group. Most preferably both Rf13 and Rf14 are fluorine.
R403, R404, R405, R406 and R407 are each independently a C1-C20 monovalent hydrocarbon group which may contain a heteroatom. Any two of R403, R404 and R405 may bond together to form a ring with the sulfur atom to which they are attached. The monovalent hydrocarbon group may be straight, branched or cyclic and examples thereof include C1-C12 alkyl groups, C2-C12 alkenyl groups, C2-C12 alkynyl groups, C6-C20 aryl groups, and C1-C12 aralkyl groups. In these groups, some or all hydrogen may be substituted by hydroxyl, carboxyl, halogen, cyano, amide, nitro, mercapto, sultone, sulfone, or sulfonium salt-containing moiety; or some carbon may be replaced by an ether bond, ester bond, carbonyl, carbonate or sulfonic acid ester bond.
The subscript r is an integer of 1 to 3. The subscript s is an integer of 1 to 5, and t is an integer of 0 to 3, meeting 1≤s+t≤5. Preferably, s is an integer of 1 to 3, more preferably 2 or 3, and t is an integer of 0 to 2.
The cation moiety in the sulfonium salt having formula (3-1) is as exemplified above for the cation moiety in the sulfonium salt having formula (1-1). The cation moiety in the iodonium salt having formula (3-2) is as exemplified above for the cation moiety in the iodonium salt having formula (1-2).
Examples of the anion moiety in the onium salts having formulae (3-1) and (3-2) are given below, but not limited thereto. Herein X is as defined above.
Figure US11500289-20221115-C00134
Figure US11500289-20221115-C00135
Figure US11500289-20221115-C00136
Figure US11500289-20221115-C00137
Figure US11500289-20221115-C00138
Figure US11500289-20221115-C00139
Figure US11500289-20221115-C00140
Figure US11500289-20221115-C00141
Figure US11500289-20221115-C00142
Figure US11500289-20221115-C00143
Figure US11500289-20221115-C00144
Figure US11500289-20221115-C00145
Figure US11500289-20221115-C00146
Figure US11500289-20221115-C00147
Figure US11500289-20221115-C00148
Figure US11500289-20221115-C00149
Figure US11500289-20221115-C00150
Figure US11500289-20221115-C00151
Figure US11500289-20221115-C00152
Figure US11500289-20221115-C00153
Figure US11500289-20221115-C00154
Figure US11500289-20221115-C00155
Figure US11500289-20221115-C00156
Figure US11500289-20221115-C00157
Figure US11500289-20221115-C00158
Figure US11500289-20221115-C00159
Figure US11500289-20221115-C00160
Figure US11500289-20221115-C00161
Figure US11500289-20221115-C00162
Figure US11500289-20221115-C00163
Figure US11500289-20221115-C00164
Figure US11500289-20221115-C00165
Figure US11500289-20221115-C00166
Figure US11500289-20221115-C00167
Figure US11500289-20221115-C00168
Figure US11500289-20221115-C00169
Figure US11500289-20221115-C00170
Figure US11500289-20221115-C00171
Figure US11500289-20221115-C00172
Figure US11500289-20221115-C00173
Figure US11500289-20221115-C00174
Figure US11500289-20221115-C00175
Figure US11500289-20221115-C00176
Figure US11500289-20221115-C00177
Figure US11500289-20221115-C00178
Figure US11500289-20221115-C00179
Figure US11500289-20221115-C00180
Figure US11500289-20221115-C00181
Figure US11500289-20221115-C00182
Figure US11500289-20221115-C00183
Figure US11500289-20221115-C00184
Figure US11500289-20221115-C00185
Figure US11500289-20221115-C00186
Figure US11500289-20221115-C00187
Figure US11500289-20221115-C00188
Figure US11500289-20221115-C00189
Figure US11500289-20221115-C00190
Figure US11500289-20221115-C00191
Figure US11500289-20221115-C00192
Figure US11500289-20221115-C00193
Figure US11500289-20221115-C00194
Figure US11500289-20221115-C00195
In the positive resist composition, the acid generator of addition type is preferably used in an amount of 0.1 to 50 parts, more preferably 1 to 40 parts by weight per 100 parts by weight of the base polymer. When the base polymer contains recurring units (d1) to (d3) and/or the acid generator of addition type is added, the positive resist composition functions as a chemically amplified positive resist composition.
Organic Solvent
The positive resist composition may contain an organic solvent. The organic solvent is not particularly limited as long as the foregoing components and other components are dissolvable therein. Examples of the organic solvent used herein are described in U.S. Pat. No. 7,537,880 (JP-A 2008-111103, paragraphs [0144]-[0145]). Exemplary solvents include ketones such as cyclohexanone, cyclopentanone and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, l-ethoxy-2-propanol, and diacetone alcohol (DAA); ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, and propylene glycol mono-t-butyl ether acetate: and lactones such as γ-butyrolactone, and mixtures thereof.
The organic solvent is preferably added in an amount of 100 to 10,000 parts, and more preferably 200 to 8,000 parts by weight per 100 parts by weight of the base polymer.
Quencher
In the positive resist composition, a quencher may be blended. The quencher is typically selected from conventional basic compounds. Conventional basic compounds include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds with carboxyl group, nitrogen-containing compounds with sulfonyl group, nitrogen-containing compounds with hydroxyl group, nitrogen-containing compounds with hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and carbamate derivatives. Also included are primary, secondary, and tertiary amine compounds, specifically amine compounds having a hydroxyl, ether bond, ester bond, lactone ring, cyano, or sulfonic acid ester bond as described in JP-A 2008-111103, paragraphs [0146]-[0164], and compounds having a carbamate group as described in JP 3790649. Addition of a basic compound may be effective for further suppressing the diffusion rate of acid in the resist film or correcting the pattern profile.
Suitable quenchers also include onium salts such as sulfonium salts, iodonium salts and ammonium salts of sulfonic acids which are not fluorinated at α-position and similar onium salts of carboxylic acid, as described in JP-A 2008-158339. While an α-fluorinated sulfonic acid, imide acid, and methide acid are necessary to deprotect the acid labile group of carboxylic acid ester, an α-non-fluorinated sulfonic acid or a carboxylic acid is released by salt exchange with an α-non-fluorinated onium salt. An α-non-fluorinated sulfonic acid and a carboxylic acid function as a quencher because they do not induce deprotection reaction.
Also useful are quenchers of polymer type as described in U.S. Pat. No. 7,598,016 (JP-A 2008-239918). The polymeric quencher segregates at the resist surface after coating and thus enhances the rectangularity of resist pattern. When a protective film is applied as is often the case in the immersion lithography, the polymeric quencher is also effective for preventing a film thickness loss of resist pattern or rounding of pattern top.
In the resist composition, the quencher is preferably added in an amount of 0 to 5 parts, more preferably 0 to 4 parts by weight per 100 parts by weight of the base polymer. The quenchers may be used alone or in admixture.
Other Components
In addition to the foregoing components, other components such as surfactant and dissolution inhibitor may be blended in any desired combination to formulate a positive resist composition. This positive resist composition has a very high sensitivity in that the dissolution rate in developer of the base polymer in exposed areas is accelerated by catalytic reaction. In addition, the resist film has a high dissolution contrast, resolution, exposure latitude, and process adaptability, and provides a good pattern profile after exposure, and minimal proximity bias because of restrained acid diffusion. By virtue of these advantages, the composition is fully useful in commercial application and suited as a pattern-forming material for the fabrication of VLSIs.
Exemplary surfactants are described in JP-A 2008-111103, paragraphs [0165]-[0166]. Inclusion of a surfactant may improve or control the coating characteristics of the resist composition. The surfactant may be used alone or in admixture. The surfactant is preferably added in an amount of 0.0001 to 10 parts by weight per 100 parts by weight of the base polymer.
The inclusion of a dissolution inhibitor may lead to an increased difference in dissolution rate between exposed and unexposed areas and a further improvement in resolution.
The dissolution inhibitor which can be used herein is a compound having at least two phenolic hydroxyl groups on the molecule, in which an average of from 0 to 100 mol % of all the hydrogen atoms on the phenolic hydroxyl groups are replaced by acid labile groups or a compound having at least one carboxyl group on the molecule, in which an average of 50 to 100 mol % of all the hydrogen atoms on the carboxyl groups are replaced by acid labile groups, both the compounds having a molecular weight of 100 to 1,000, and preferably 150 to 800. Typical are bisphenol A, trisphenol, phenolphthalein, cresol novolac, naphthalenecarboxylic acid, adamantanecarboxylic acid, and cholic acid derivatives in which the hydrogen atom on the hydroxyl or carboxyl group is replaced by an acid labile group, as described in U.S. Pat. No. 7,771,914 (JP-A 2008-122932, paragraphs [0155]-[0178]).
The dissolution inhibitor is preferably added in an amount of 0 to 50 parts, more preferably 5 to 40 parts by weight per 100 parts by weight of the base polymer.
To the resist composition, a polymeric additive (or water repellency improver) may also be added for improving the water repellency on surface of a resist film as spin coated. The water repellency improver may be used in the topcoatless immersion lithography.
Suitable water repellency improvers include polymers having a fluoroalkyl group and polymers having a specific structure with a 1,1,1,3,3,3-hexafluoro-2-propanol residue and are described in JP-A 2007-297590 and JP-A 2008-111103, for example. The water repellency improver to be added to the resist composition should be soluble in the organic solvent as the developer. The water repellency improver of specific structure with a 1,1,1,3,3,3-hexafluoro-2-propanol residue is well soluble in the developer. A polymer having an amino group or amine salt copolymerized as recurring units may serve as the water repellent additive and is effective for preventing evaporation of acid during PEB, thus preventing any hole pattern opening failure after development. An appropriate amount of the water repellency improver is 0 to 20 parts, preferably 0.5 to 10 parts by weight per 100 parts by weight of the base polymer.
Also, an acetylene alcohol may be blended in the resist composition. Suitable acetylene alcohols are described in JP-A 2008-122932, paragraphs [0179]-[0182]. An appropriate amount of the acetylene alcohol blended is 0 to 5 parts by weight per 100 parts by weight of the base polymer.
Process
The positive resist composition is used in the fabrication of various integrated circuits. Pattern formation using the resist composition may be performed by well-known lithography processes. The process generally involves coating, exposure, and development. If necessary, any additional steps may be added.
For example, the positive resist composition is first applied onto a substrate on which an integrated circuit is to be formed (e.g., Si. SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, or organic antireflective coating) or a substrate on which a mask circuit is to be formed (e.g., Cr, CrO, CrON, MoSi2, or SiO2) by a suitable coating technique such as spin coating, roll coating, flow coating, dipping, spraying or doctor coating. The coating is prebaked on a hotplate at a temperature of 60 to 150° C. for 10 seconds to 30 minutes, preferably at 80 to 120° C. for 30 seconds to 20 minutes. The resulting resist film is generally 0.01 to 2 μm thick.
The resist film is then exposed to a desired pattern of high-energy radiation such as UV, deep-UV, EB, EUV of wavelength 3 to 15 nm, x-ray, soft x-ray, excimer laser light, γ-ray or synchrotron radiation. When UV, deep-UV, EUV, x-ray, soft x-ray, excimer laser light, γ-ray or synchrotron radiation is used as the high-energy radiation, the resist film is exposed thereto through a mask having a desired pattern in a dose of preferably about 1 to 200 mJ/cm2, more preferably about 10 to 100 mJ/cm2. When EB is used as the high-energy radiation, the resist film is exposed thereto through a mask having a desired pattern or directly in a dose of preferably about 0.1 to 100 μC/cm2, more preferably about 0.5 to 50 μC/cm2. It is appreciated that the inventive resist composition is suited in micropatterning using KrF excimer laser, ArF excimer laser, EB, EUV, x-ray, soft x-ray, γ-ray or synchrotron radiation, especially in micropatterning using EB or EUV.
After the exposure, the resist film may be baked (PEB) on a hot plate at 60 to 150° C. for 10 seconds to 30 minutes, preferably at 80 to 120° C. for 30 seconds to 20 minutes.
After the exposure or PEB, the resist film is developed in a developer in the form of an aqueous base solution for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes by conventional techniques such as dip, puddle and spray techniques. A typical developer is a 0.1 to 10 wt %, preferably 2 to 5 wt % aqueous solution of tetramnethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), or tetrabutylammonium hydroxide (TBAH). The resist film in the exposed area is dissolved in the developer whereas the resist film in the unexposed area is not dissolved. In this way, the desired positive pattern is formed on the substrate.
In an alternative embodiment, a negative pattern may be formed via organic solvent development using a positive resist composition comprising a base polymer having an acid labile group. The developer used herein is preferably selected from among 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate, and mixtures thereof.
At the end of development, the resist film is rinsed. As the rinsing liquid, a solvent which is miscible with the developer and does not dissolve the resist film is preferred. Suitable solvents include alcohols of 3 to 10 carbon atoms, ether compounds of 8 to 12 carbon atoms, alkanes, alkenes, and alkynes of 6 to 12 carbon atoms, and aromatic solvents. Specifically, suitable alcohols of 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-1-pentaol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol. Suitable ether compounds of 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-s-butyl ether, di-n-pentyl ether, diisopentyl ether, di-s-pentyl ether, di-t-pentyl ether, and di-n-hexyl ether. Suitable alkanes of 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane. Suitable alkenes of 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene. Suitable alkynes of 6 to 12 carbon atoms include hexyne, heptyne, and octyne. Suitable aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, t-butylbenzene and mesitylene.
Rinsing is effective for minimizing the risks of resist pattern collapse and defect formation. However, rinsing is not essential. If rinsing is omitted, the amount of solvent used may be reduced.
A hole or trench pattern after development may be shrunk by the thermal flow, RELACS® or DSA process. A hole pattern is shrunk by coating a shrink agent thereto, and baking such that the shrink agent may undergo crosslinking at the resist surface as a result of the acid catalyst diffusing from the resist layer during bake, and the shrink agent may attach to the sidewall of the hole pattern. The bake is preferably at a temperature of 70 to 180° C., more preferably 80 to 170° C., for a time of 10 to 300 seconds. The extra shrink agent is stripped and the hole pattern is shrunk.
EXAMPLES
Examples of the invention are given below by way of illustration and not by way of limitation. All parts are by weight (pbw). Mw and Mw/Mn are determined by GPC versus polystyrene standards using THF solvent.
[1] Synthesis of Monomers Synthesis Example 1-1
Synthesis of Monomer 1
In 50 g of THF were dissolved 11.5 g of 2-azetidin-3-yl-propan-2-ol and 0.4 g of 4-(dimethylamino)pyridine. Under ice cooling, 18.5 g of methacrylic anhydride was added dropwise to the solution. The solution was stirred at room temperature for 5 hours, after which water was added to quench the reaction. The reaction solution was subjected to standard aqueous workup and purified by silica gel column chromatography, obtaining Monomer 1 of the following formula.
Figure US11500289-20221115-C00196
Synthesis Example 1-2
Synthesis of Monomer 2
Monomer 2 of the following formula was obtained by the same procedure as in Synthesis Example 1-1 aside from using 14.3 g of 2-(4-piperidyl)-2-propanol instead of 2-azetidin-3-yl-propan-2-ol.
Figure US11500289-20221115-C00197
Synthesis Example 1-3
Synthesis of Monomer 3
Monomer 3 of the following formula was obtained by the same procedure as in Synthesis Example 1-1 aside from using 12.9 g of 1,4-dimethyl-4-piperidinol instead of 2-azetidin-3-yl-propen-2-ol.
Figure US11500289-20221115-C00198
Synthesis Example 1-4
Synthesis of Monomer 4
Monomer 4 of the following formula was obtained by the same procedure as in Synthesis Example 1-1 aside from using 13.9 g of 4-ethynyl-1-methyl-4-piperidinol instead of 2-azetidin-3-yl-propan-2-ol.
Figure US11500289-20221115-C00199
Synthesis Example 1-5
Synthesis of Monomer 5
Monomer 5 of the following formula was obtained by the same procedure as in Synthesis Example 1-1 aside from using 11.5 g of 3-methylpiperidin-3-ol instead of 2-azetidin-3-yl-propan-2-ol.
Figure US11500289-20221115-C00200
Synthesis Example 1-6
Synthesis of Monomer 6
Monomer 6 of the following formula was obtained by the same procedure as in Synthesis Example 1-1 aside from using 24.3 g of 2-(4-tert-butoxycarbonylpiperidyl)-2-propanol instead of 2-azetidin-3-yl-propau-2-ol.
Figure US11500289-20221115-C00201
[2] Synthesis of Polymers
PAG Monomers 1 to 3 identified below were used in the synthesis of polymers.
Figure US11500289-20221115-C00202
Synthesis Example 2-1
Synthesis of Polymer 1
A 2-L flask was charged with 2.1 g of Monomer 2, 8.4 g of l-methyl-1-cyclopentyl methacrylate, 4.8 g of 4-hydroxystyrene, and 40 g of tetrahydrofuran (THF) as solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of azobisisobutyronitrile (AIBN) was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The precipitated white solid was collected by filtration and vacuum dried at 60° C., yielding Polymer 1. Polymer 1 was analyzed for composition by 13C- and 1H-NMR and for Mw and Mw/Mn by GPC.
Figure US11500289-20221115-C00203
Synthesis Example 2-2
Synthesis of Polymer 2
A 2-L flask was charged with 1.8 g of Monomer 1, 7.3 g of 1-methyl-1-cyclohexyl methacrylate, 4.2 g of 4-hydroxystyrene, 11.9 g of PAG Monomer 1, and 40 g of THF as solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of AIBN was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The precipitated white solid was collected by filtration and vacuum dried at 60° C., yielding Polymer 2. Polymer 2 was analyzed for composition by 13C- and 1H-NMR and for Mw and Mw/Mn by GPC.
Figure US11500289-20221115-C00204
Synthesis Example 2-3
Synthesis of Polymer 3
A 2-L flask was charged with 1.9 g of Monomer 3, 5.2 g of 1-(cyclopropyl-1-yl)-1-methylethyl methacrylate, 3.5 g of 3-fluoro-4-(methylcyclohexyloxy)styrene, 4.8 g of 3-hydroxystyrene, 11.2 g of PAG Monomer 3, and 40 g of THF as solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of AIBN was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The precipitated white solid was collected by filtration and vacuum dried at 60° C. yielding Polymer 3. Polymer 3 was analyzed for composition by 13C- and 1H-NMR and for Mw and Mw/Mn by GPC.
Figure US11500289-20221115-C00205
Synthesis Example 2-4
Synthesis of Polymer 4
A 2-L flask was charged with 2.5 g of Monomer 4, 6.4 g of 1-methyl-1-cyclopentyl methacrylate, 4.2 g of 4-hydroxystyrene, 11.0 g of PAG Monomer 2, and 40 g of THF as solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of AIBN was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The precipitated white solid was collected by filtration and vacuum dried at 60° C., yielding Polymer 4. Polymer 4 was analyzed for composition by 13C- and 1H-NMR and for Mw and Mw/Mn by GPC.
Figure US11500289-20221115-C00206
Synthesis Example 2-5
Synthesis of Polymer 5
A 2-L flask was charged with 1.5 g of Monomer 5, 7.1 g of l-ethyl-1-cyclopentyl methacrylate, 4.2 g of 4-hydroxystyrene, 11.0 g of PAG Monomer 2, and 40 g of THF as solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of AIBN was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The precipitated white solid was collected by filtration and vacuum dried at 60° C., yielding Polymer 5. Polymer 5 was analyzed for composition by 13C- and 1H-NMR and for Mw and Mw/Mn by GPC.
Figure US11500289-20221115-C00207
Synthesis Example 2-6
Synthesis of Polymer 6
A 2-L flask was charged with 3.1 g of Monomer 6, 8.4 g of 1-methyl-1-cyclopentyl methacrylate, 4.8 g of 4-hydroxystyrene, and 40 g of THF as solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of AIBN was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The precipitated white solid was collected by filtration and vacuum dried at 60° C., yielding to Polymer 6. Polymer 6 was analyzed for composition by 1C- and 1H-NMR and for Mw and Mw/Mn by GPC.
Figure US11500289-20221115-C00208
Synthesis Example 2-7
Synthesis of Polymer 7
A 2-L flask was charged with 2.5 g of Monomer 6, 7.1 g of l-ethyl-1-cyclopentyl methacrylate, 4.2 g of 4-hydroxystyrene, 11.0 g of PAG Monomer 2, and 40 g of THF as solvent. The reactor was cooled at −70° C. in nitrogen atmosphere, after which vacuum pumping and nitrogen blow were repeated three times. The reactor was warmed up to room temperature, whereupon 1.2 g of AIBN was added. The reactor was heated at 60° C., whereupon reaction ran for 15 hours. The reaction solution was poured into 1 L of isopropyl alcohol for precipitation. The precipitated white solid was collected by filtration and vacuum dried at 60° C., yielding Polymer 7. Polymer 7 was analyzed for composition by 13C- and 1H-NMR and for Mw and Mw/Mn by GPC.
Figure US11500289-20221115-C00209
Comparative Synthesis Example 1
Comparative Polymer 1 was obtained by the same procedure as in Synthesis Example 2-1 except that Monomer 1 was omitted. Comparative Polymer 1 was analyzed for composition by 13C- and 1H-NMR and for Mw and Mw/Mn by GPC.
Figure US11500289-20221115-C00210
Comparative Synthesis Example 2
Comparative Polymer 2 was obtained by the same procedure as in Synthesis Example 2-1 except that 2-(dimethylamino)ethyl methacrylate was used instead of Monomer 1. Comparative Polymer 2 was analyzed for composition by 13C- and 1H-NMR and for Mw and Mw/Mn by GPC.
Figure US11500289-20221115-C00211
Comparative Synthesis Example 3
Comparative Polymer 3 was obtained by the same procedure as in Synthesis Example 2-4 except that Monomer 4 was omitted. Comparative Polymer 3 was analyzed for composition by 13C- and 1H-NMR and for Mw and Mw/Mn by GPC.
Figure US11500289-20221115-C00212
[3] Preparation and Evaluation of Positive Resist Composition
Examples 1 to 12 and Comparative Examples 1 to 3
Positive resist compositions were prepared by dissolving components in a solvent in accordance with the recipe shown in Table 1, and filtering through a filter having a pore size of 0.2 μm. The solvent contained 100 ppm of surfactant FC-4430 (3M). The components in Table 1 are as identified below.
Organic Solvents:
PGMEA (propylene glycol monomethyl ether acetate)
DAA (diacetone alcohol)
Acid generator: PAG 1 of the following structural formula
Quencher: Q-1 to Q-4 of the following structural formulae
Figure US11500289-20221115-C00213
EUV Lithography Test
Each of the resist compositions in Table 1 was spin coated on a silicon substrate having a 20-nm coating of silicon-containing spin-on hard mask SHB-A940 (Shin-Etsu Chemical Co., Ltd., Si content 43 wt %) and prebaked on a hotplate at 105° C. for 60 seconds to form a resist film of 60 nm thick. Using an EUV scanner NXE3300 (ASML, NA 0.33, σ0.9/0.6, quadrupole illumination), the resist film was exposed to EUV through a mask bearing a hole pattern at a pitch 46 nm (on-wafer size) and +20% bias. The resist film was baked (PEB) on a hotplate at the temperature shown in Table 1 for 60 seconds and developed in a 2.38 wt % TMAH aqueous solution for 30 seconds to form a hole pattern having a size of 23 nm.
The resist pattern was observed under CD-SEM (CG-5000, Hitachi High-Tedmologies Corp.). The exposure dose that provides a hole pattern having a size of 23 nm is reported as sensitivity. The size of 50 holes was measured, from which a size variation (3c) was computed and reported as CDU.
The resist composition is shown in Table 1 together with the sensitivity and CDU of EUV lithography.
TABLE 1
Polymer Acid generator Quencher Organic solvent PEB temp. Sensitivity CDU
(pbw) (pbw) (pbw) (pbw) (° C.) (mJ/cm2) (nm)
Example 1 Polymer 1 PAG 1 — PGMEA (2,000) 95 29 3.0
(100) (25.0) DAA (500)
2 Polymer 2 — — PGMEA (2,000) 95 26 2.7
(100) DAA (500)
3 Polymer 3 — — PGMEA (2,000) 95 27 2.6
(100) DAA (500)
4 Polymer 4 — — PGMEA (2,000) 95 28 2.3
(100) DAA (500)
5 Polymer 5 — — PGMEA (2,000) 95 28 2.6
(100) DAA (500)
6 Polymer 5 — Q-1 PGMEA (2,000) 95 35 2.0
(100) (1.00) DAA (500)
7 Polymer 5 PAG 1 Q-1 PGMEA (2,000) 95 22 2.3
(100) (10.0) (1.00) DAA (500)
8 Polymer 6 PAG 1 — PGMEA (2,000) 95 29 3.0
(100) (25.0) DAA (500)
9 Polymer 7 — — PGMEA (2,000) 95 29 2.4
(100) DAA (500)
10 Polymer 7 — Q-3 PGMEA (2,000) 95 31 2.0
(100) (1.50) DAA (500)
11 Polymer 7 — Q-4 PGMEA (2,000) 95 36 2.1
(100) (1.20) DAA (500)
12 Polymer 7 — Q-4 PGMEA (2,000) 95 38 2.2
(70) (1.20) DAA (500)
Comparative
Polymer 3
(30)
Comparative 1 Comparative PAG 1 Q-2 PGMEA (2,000) 95 30 5.6
Example Polymer 1 (25.0) (3.00) DAA (500)
(100)
2 Comparative PAG 1 — PGMEA (2,000) 95 38 4.7
Polymer 2 (25.0) DAA (500)
(100)
3 Comparative — Q-1 PGMEA (2,000) 95 35 3.9
Polymer 3 (3.00) DAA (500)
(100)
It is demonstrated in Table 1 that positive resist compositions comprising a base polymer comprising recurring units having a nitrogen-containing tertiary ester structure offer a high sensitivity and improved CDU.
Japanese Patent Application No. 2018-234513 is incorporated herein by reference.
Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.

Claims (13)

The invention claimed is:
1. A positive resist composition comprising a base polymer comprising recurring units having the formula (a):
Figure US11500289-20221115-C00214
wherein RA is hydrogen or methyl, X1 is each independently a single bond, phenylene, naphthylene, or a C1-C12 linking group containing an ester bond, ether bond or lactone ring, and R is a nitrogen-containing tertiary hydrocarbon group having the formula (a1) or (a2):
Figure US11500289-20221115-C00215
wherein R1 and R2 are each independently a C1-C6 alkyl group, C2-C6 alkenyl group or C2-C6 alkynyl group, R1 and R2 may bond together to form a ring with the carbon atom to which they are attached, R3 and R5 are each independently hydrogen, a C1-C9 straight, branched or cyclic alkyl group, C2-C10 straight or branched alkoxycarbonyl group, C3-C10 straight or branched alkenyloxycarbonyl group, or C8-C14 aralkyloxycarbonyl group, the group optionally containing an ether bond, R4 is a C1-C6 alkyl group, C2-C6 alkenyl group or C2-C6 alkynyl group, the circle Ra is a C2-C10 alicyclic group including the nitrogen atom, and the broken line designates a valence bond to the oxygen atom in formula (a).
2. The positive resist composition of claim 1 wherein the base polymer further comprises recurring units having a carboxyl group in which the hydrogen is substituted by an acid labile group and/or recurring units having a phenolic hydroxyl group in which the hydrogen is substituted by an acid labile group.
3. The positive resist composition of claim 2 wherein the recurring units having a carboxyl group in which the hydrogen is substituted by an acid labile group and the recurring units having a phenolic hydroxyl group in which the hydrogen is substituted by an acid labile group are recurring units having the formula (b1) and recurring units having the formula (b2), respectively,
Figure US11500289-20221115-C00216
wherein RA is each independently hydrogen or methyl, Y1 is a single bond, phenylene, naphthylene, or a C1-C12 linking group containing an ester bond, ether bond or lactone ring, Y2 is a single bond, ester bond or amide bond, R11 and R12 each are an acid labile group, R13 is fluorine, trifluoromethyl, cyano or C1-C6 alkyl, R14 is a single bond or a C1-C6 straight or branched alkanediyl group in which some carbon may be replaced by an ether bond or ester bond, a is 1 or 2, and b is an integer of 0 to 4.
4. The positive resist composition of claim 1 wherein the base polymer further comprises recurring units containing an adhesive group selected from the group consisting of hydroxyl, carboxyl, lactone ring, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether bond, ester bond, sulfonic ester bond, cyano, amide, —O—C(═O)—S—, and —O—C(═O)—NH—.
5. The positive resist composition of claim 1 wherein the base polymer further comprises recurring units of at least one type selected from recurring units having the formulae (d1) to (d3):
Figure US11500289-20221115-C00217
wherein RA is each independently hydrogen or methyl,
Z1 is a single bond, phenylene, O—Z11—, —C(═O)—O—Z11— or —C(═O)—NH—Z11—, Z11 is a C1-C6 alkanediyl group, C2-C6 alkenediyl group, or phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxyl moiety,
Z2 is a single bond or a C1-C12 divalent group which may contain an ester bond, ether bond or lactone ring,
Z3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—Z31—, —C(═O)—O—Z31— or —C(═O)—NH—Z31 is a C1-C6 alkanediyl group, C2-C6 alkenediyl group, or phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxyl moiety,
Rf1 to Rf4 are each independently hydrogen, fluorine or trifluoromethyl, at least one of Rf1 to Rf4 being fluorine,
R21 to R28 are each independently a C1-C20 monovalent hydrocarbon group which may contain a heteroatom, any two of R23, R24 and R25 or any two of R26, R27 and R28 may bond together to form a ring with the sulfur atom to which they are attached, and M is a non-nucleophilic counter ion.
6. The positive resist composition of claim 1, further comprising an acid generator.
7. The positive resist composition of claim 1, further comprising an organic solvent.
8. The positive resist composition of claim 1, further comprising a quencher.
9. The positive resist composition of claim 1, further comprising a surfactant.
10. The positive resist composition of claim 1 wherein the monomers from which recurring units (a) having a group of formula (a2) are derived are selected from the group consisting of the following formulae:
Figure US11500289-20221115-C00218
Figure US11500289-20221115-C00219
Figure US11500289-20221115-C00220
11. The resist composition of claim 1 wherein R is a nitrogen-containing tertiary hydrocarbon group having the formula (a1).
12. A pattern forming process comprising the steps of applying the positive resist composition of claim 1 to form a resist film on a substrate, exposing the resist film to high-energy radiation, and developing the exposed resist film in a developer.
13. The pattern forming process of claim 12 wherein the high-energy radiation is i-line, KrF excimer laser, ArF excimer laser, EB, or EUV of wavelength 3 to 15 nm.
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